Explosive compositions using a combination of emulsifying salts

ABSTRACT

The present invention provides for an explosive composition comprising a discontinuous oxidizer phase comprising at least one oxygen-supplying component, a continuous organic phase comprising at least carbonaceous fuel, and an emulsifying amount of (A) at least one salt composition derived from (A) (I) at least one high-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of (A) (I) having an average of from about 20 to about 500 carbon atoms, and (A) (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound; and (B) at least one salt composition derived from (B) (I) at least one low-molecular weight hydrocarbyl-substituted carboxylic acid or anhydride, or ester or amide derivative of said acid or anhydride, the hydrocarbyl substituent of (B) (I) having an average of from about 8 to about 18 carbon atoms, and (B) (II) ammonia, at least one amine, at least one alkali or alkaline earth metal, and/or at least one alkali or alkaline earth metal compound.

TECHNICAL FIELD

This invention relates to explosive compositions employing a combinationof low- and high-molecular weight emulsifying salts. These explosivecompositions are water-in-oil explosive emulsions which, in oneembodiment, are cap-sensitive explosive emulsions.

BACKGROUND OF THE INVENTION

Hydrocarbyl-substituted carboxylic acylating agents having at leastabout 30 aliphatic carbon atoms in the substituent are known. Examplesof such acylating agents include the polyisobutenyl-substituted succinicacids and anhydrides. The use of such carboxylic acylating agents asadditives in normally liquid fuels and lubricants is disclosed in U.S.Pat. Nos. 3,288,714 and 3,346,354. These acylating agents are alsouseful as intermediates for preparing additives for use in normallyliquid fuels and lubricants as described in U.S. Pat. Nos. 2,892,786;3,087,936; 3,163,603; 3,172,892; 3,189,544; 3,215,707; 3,219,666;3,231,587; 3,235,503; 3,272,746; 3,306,907; 3,306,908; 3,331,776;3,341,542; 3,346,354; 3,374,174; 3,379,515; 3,381,022; 3,413,104;3,450,715; 3,454,607; 3,455,728; 3,476,686; 3,513,095; 3,523,768;3,630,904; 3,632,511; 3,697,428; 3,755,169; 3,804,763; 3,836,470;3,862,981; 3,936,480; 3,948,909; 3,950,341; 4,234,435; and 4,471,091;and French Pat. No. 2,223,415.

U.S. Pat. No. 3,216,936 describes nitrogen-containing dispersants foruse in lubricants which are obtained by the reaction of an alkyleneamine with an acidic mixture consisting of a hydrocarbon-substitutedsuccinic acid having at least about 50 aliphatic carbon atoms in thehydrocarbon substituent and an aliphatic monocarboxylic acid. Thealiphatic monocarboxylic acids are described as including saturated andunsaturated acids such as acetic acid, dodecanoic acid, oleic acid,naphthenic acid, formic acid, etc. Acids having 12 or more aliphaticcarbon atoms, particularly stearic acid and oleic acid, are described asbeing especially useful.

U.S. Pat. Nos. 3,639,242 and 3,708,522 describe compositions prepared bypost-treating mono- and polycarboxylic acid esters with mono- orpolycarboxylic acid acylating agents. The compositions thus obtained arereported to be useful as dispersants in lubricants and fuels.

U.S. Pat. No. 4,642,330 discloses dispersant salt compositions made byreacting phosphorus-free carboxylic solubilizers with sulfonic acid-freeorganic acids or mineral acids. The carboxylic solubilizer is thereaction product of a polycarboxylic acid acylating agent having atleast one hydrocarbon-based substituent of at least 8 to 500 carbonatoms with at least one poly(alkyleneamine). The reference indicatesthat these dispersant salt compositions have good thermal stability whenmixed with a surfactant or a hydrophilic organic solvent, and that theycan be used with aqueous solutions to disperse various fillers includingcarbon black and to solubilize various fluids.

Nitrogen-containing, phosphorus-free carboxylic solubilizers useful inwater based functional fluids are disclosed in U.S. Pat. Nos. 4,329,249;4,368,133; 4,435,297; 4,447,348; and 4,448,703. These solubilizers aremade by reacting (I) at least one carboxylic acid acylating agent havingat least one hydrocarbyl substituent of from about 12 to about 500carbon atoms with (II) at least one (a) N-(hydroxyl-substitutedhydrocarbyl) amine, (b) hydroxyl-substituted poly(hydrocarbyloxy) analogof said amine (a), or (c) mixtures of (a) and (b). These patentsindicate that preferred acylating agents include the substitutedsuccinic acids or anhydrides, such as polyisobutenyl-substitutedsuccinic anhydride, and that the amines that are useful include theprimary, secondary and tertiary alkanol amines, such asdiethylethanolamine and mixtures of diethylethanolamine andethanolamine. These solubilizers are useful in dispersing oil-soluble,water-insoluble functional additives in water-based functional fluids.

Water-in-oil explosive emulsions typically comprise a continuous organicphase and a discontinuous oxidizer phase containing water and anoxygen-supplying source such as ammonium nitrate, the oxidizer phasebeing dispersed throughout the continuous organic phase. Examples ofsuch water-in-oil explosive emulsions are disclosed, inter alia, in U.S.Pat. Nos. 3,447,978; 3,765,964; 3,985,593; 4,008,110; 4,097,316;4,104,092; 4,218,272; 4,259,977; 4,357,184; 4,371,408; 4,391,659;4,404,050; 4,409,044; 4,448,619; 4,453,989; and 4,534,809; U.K. PatentApplication No. GB 2,050,340A; and European Application Publication No.0,156,572.

European Application No. 0,155,800 discloses an explosive emulsioncomposition comprising a descontinuous phase containing anoxygen-supplying component and an organic medium forming a continuousphase wherein the oxygen-supplying component and organic medium arecapable of forming an emulsion which, in the absence of a supplementaryadjuvant, exhibits an electrical conductivity measured at 60° C., notexceeding 60,000 picomhos/meter. The reference indicates that theconductivity may be achieved by the inclusion of a modifier which alsofunctions as an emulsifier. The modifier is comprised of a hydrophilicmoiety and a lipophilic moiety. The lipophilic moiety can be derivedfrom a poly[alk(en)yl] succinic anhydride. Poly(isobutylene) succinicanhydride having a number average molecular weight in the range of 400to 5000 is specifically identified as being useful. The hydrophilicmoiety is described as being polar in character, having a molecularweight not exceeding 450 and can be derived from polyols, amines,amides, alkanol amines and heterocyclics. Example 14 of this referencediscloses the use of a 1:1 condensate polyisobutenyl succinic anhydride(number average molecular weight=1200) and N, N-dimethylamino ethanol asthe modifier.

Cap-sensitive explosive emulsions are water-in-oil explosive emulsionswhich can be detonated without the use of a booster. Examples of suchcap-sensitive explosive emulsions are disclosed, inter alia, in U.S.Pat. Nos. 3,715,247; 4,110,134; 4,149,916; 4,149,917; 4,231,821;3,383,873; 4,394,198; and 4,490,195.

SUMMARY OF THE INVENTION

The present invention provides for an explosive composition comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least carbonaceousfuel, and an emulsifying amount of (A) at least one salt compositionderived from (A)(I) at least one high-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederivative of said acid or anhydride, the hydrocarbyl substituent of(A)(I) having an average of from about 20 to about 500 carbon atoms, and(A)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound; and (B) at least one salt composition derived from (B)(I) atleast one low-molecular weight hydrocarbyl-substituted carboxylic acidor anhydride, or ester or amide derivative of said acid or anhydride,the hydrocarbyl substituent of (B)(I) having an average of from about 8to about 18 carbon atoms, and (B)(II) ammonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term "emulsion" as used in this specification and in the appendedclaims is intended to cover not only water-in-oil emulsions, but alsocompositions derived from such emulsions wherein at temperatures belowthat at which the emulsion is formed the discontinuous phase is solid orin the form of droplets of super-cooled liquid. This term also coverscompositions derived from or formulated as such water-in-oil emulsionsthat are in the form of gelatinous or semi-gelatinous compositions.

The term "hydrocarbyl" is used herein to include:

(1) hydrocarbyl groups, that is, aliphatic (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl, cycloalkenyl), aromatic, aliphatic- andalicyclic-substituted substituted aromatic groups and the like as wellas cyclic groups wherein the ring is completed through another portionof the molecule (that is, any two indicated groups may together form analicyclic group);

(2) substituted hydrocarbyl groups, that is, those groups containingnon-hydrocarbon groups which, in the context of this invention, do notalter the predominantly hydrocarbyl nature of the hydrocarbyl group;those skilled in the art will be aware of such groups, examples of whichinclude ether, oxo, halo (e.g., chloro and fluoro), alkoxyl, mercapto,alkylmercapto, nitro, nitroso, sulfoxy, etc.;

(3) hetero groups, that is, groups which, while having predominantlyhydrocarbyl character within the context of this invention, containother than carbon in a ring or chain otherwise composed of carbon atoms.Suitable heteroatoms will be apparent to those of skill in the art andinclude, for example, sulfur, oxygen, nitrogen and such substituents aspyridyl, furanyl, thiophenyl, imidazolyl, etc.

In general, no more than about three nonhydrocarbon groups orheteroatoms and preferably no more than one, will be present for eachten carbon atoms in a hydrocarbyl group. Typically, there will be nosuch groups or heteroatoms in a hydrocarbyl group and it will,therefore, be purely hydrocarbyl.

The hydrocarbyl groups are preferably free from acetylenic unsaturation;ethylenic unsaturation, when present will generally be such that thereis no more than one ethylenic linkage present for every tencarbon-to-carbon bonds. The hydrocarbyl groups are often completelysaturated and therefore contain no ethylenic unsaturation.

The term "lower" as used herein in conjunction with terms such as alkyl,alkenyl, alkoxy, and the like, is intended to describe such groups whichcontain a total of up to 7 carbon atoms.

Components (A)(I) and (B)(I)

Components (A)(I) and (B)(I) are aliphatic or aromatic, mono- orpolycarboxylic acids or anhydrides, or ester or amide derivativesthereof. Throughout this specification and in the appended claims, theterm "carboxylic acid" is intended to include carboxylic acids as wellas acid-producing derivatives thereof such as anhydrides, acyl halidesand mixtures thereof, unless otherwise specifically stated.

Components (A)(I) and (B)(I) may contain polar substituents providedthat the polar substituent are not present in portions sufficientlylarge to alter significantly the hydrocarbon character of the acylatingagent. Typical suitable polar substituents include halo, such as chloroand bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro, etc. Suchpolar substituents, if present, preferably do not exceed about 10% byweight of the total weight of the hydrocarbon portion of the acylatingagent, exclusive of the carboxyl groups.

The lower molecular weight monocarboxylic acids (B)(I) contemplated foruse in this invention include saturated and unsaturated acids. Examplesof such useful acids include dodecanoic acid, palmitic acid, decanoicacid, oleic acid, lauric acid, stearic acid, myristic acid, linoleicacid, linolenic acid, naphthenic acid, chlorostearic acid, tall oilacid, etc. Anhydrides and lower alkyl esters of these acids can also beused. Mixtures of two or more of the foregoing can also be used. Anextensive discussion of these acids is found in Kirk-Othmer"Encyclopedia of Chemical Technology" Third Edition, 1978, John Wiley &Sons New York, pp. 814-871; these pages being incorporated herein byreference.

Examples of lower molecular weight polycarboxylic acids (B)(I) includedicarboxylic acids and derivatives such as cetyl malonic acid,tetrapropylene-substituted succinic anhydride, etc. Lower alkyl estersof these acids and anhydrides can also be used.

Low molecular weight hydrocarbyl-substituted succinic acid andanhydrides can also be used as component (B)(I). These succinic acidsand anhydrides can be represented by the formulae ##STR1## wherein R isa C₁ to about a C₁₈ hydrocarbyl group. Preferably, R is an aliphatic oralicyclic hydrocarbyl group with less than about 10% of itscarbon-to-carbon bonds being unsaturated. R can be derived from olefinsof from 2 to about 18 carbon atoms with alpha-olefins being particularlyuseful. Examples of such olefins include ethylene, propylene, 1-butene,isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene,1-heptene, 1-octene, styrene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,1-heptadecene, 1-octadecene, etc. Commercially available alpha olefinfractions such as C₁₅₋₁₈ alpha-olefins, C₁₂₋₁₆ alphaolefins, C₁₄₋₁₆alpha-olefins, C₁₄₋₁₈ alpha-olefins, C₁₆₋₁₈ alphaolefins, etc., areparticularly useful; these commercial alpha-olfin fractions usuallyinclude minor amounts of alpha-olefins outside the given ranges. Theproduction of such substituted succinic acids and their derivatives iswell known to those of skill in the art and need not be discussed indetail herein.

Acid halides of the afore-described low-molecular weight mono- andpolycarboxylic acids can be used as the low-molecular weight component(B)(I) of this invention. These can be prepared by the reaction of suchacids or their anhydrides with halogenating agents such as phosphorustribromide, phosphorus pentachloride, phosphorus oxychloride or thionylchloride. Esters of such acids can be prepared simply by the reaction ofthe acid, acid halide or anhydride with an alcohol, the alcohols beingdiscussed in greater detail below. Esterification reactions can bepromoted by the use of alkaline catalysts such as sodium hydroxide oralkoxide, or an acidic catalyst such as sulfuric acid or toluenesulfonic acid. These esterification reactions are discussed in greaterdetail below.

Although it is preferred that the acid (B)(I) is an aliphatic mono- orpolycarboxylic acid, and more preferably a dicarboxylic acid, thecarboxylic acid (B)(I) may also be an aromatic mono- or polycarboxylicacid or acid-producing compound. The aromatic acids are preferably mono-and dicarboxy-substituted benzene, naphthalene, anthracene, phenanthreneor like aromatic hydrocarbons. They include also the alkyl-substitutedderivatives, and the alkyl groups may contain up to about 12 carbonatoms. The aromatic acid may also contain other substituents such ashalo, hydroxy, lower alkoxy, etc. Specific examples of aromatic mono-and polycarboxylic acids and acid-producing compounds useful ascomponent (B)(I) include alkyl-substituted benzoic acid,alkyl-substituted phthalic acid, 4-propoxy-benzoic acid,4-ethyl-benzene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylicacid, anthracene dicarboxylic acid, 3-dodecyl-benzene-1,4-dicarboxylicacid, 2,5-dibutylbenzene-1,4-dicarboxylic acid, etc. The anhydrides ofthese dicarboxylic acids also are useful as component (B)(I).

The high-molecular weight mono- and polycarboxylic acids (A)(I) are wellknown in the art and have been described in detail, for example, in thefollowing U.S., British and Canadian patents: U.S. Pat. Nos. 3,024,237;3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666; 3,231,587;3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550;3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354;3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607;3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330;3,912,764; 4,234,435; and 4,368,133; British Pat. Nos. 944,136;1,085,903; 1,162,436; and 1,440,219; and Canadian Pat. No. 956,397.These patents are incorporated herein by reference.

As disclosed in the foregoing patents, there are several processes forpreparing these high-molecular weight carboxylic acids (A)(I).Generally, these processes involve the reaction of (1) an ethylenicallyunsaturated carboxylic acid, acid halide, anhydride or ester reactantwith (2) an ethylenically unsaturated hydrocarbon containing at leastabout 20 aliphatic carbon atoms or a chlorinated hydrocarbon containingat least about 20 aliphatic carbon atoms at a temperature within therange of about 100°-300° C. The chlorinated hydrocarbon or ethylenicallyunsaturated hydrocarbon reactant preferably contains at least about 30carbon atoms, more preferably at least about 40 carbon atoms, morepreferably at least about 50 carbon atoms, and may contain polarsubstituents, oil-solubilizing pendant groups, and be unsaturated withinthe general limitations explained hereinabove.

When preparing the carboxylic acid acylating agent, the carboxylic acidreactant usually corresponds to the formula R_(o) -(COOH)_(n), whereR_(o) is characterized by the presence of at least one ethylenicallyunsaturated carbon-to-carbon covalent bond and n is an integer from 1 toabout 6 and preferably is 2. The acidic reactant can also be thecorresponding carboxylic acid halide, anhydride, ester, amide or otherequivalent acylating agent and mixtures of two or more of these.Ordinarily, the total number of carbon atoms in the acidic reactant willnot exceed about 20, preferably this number will not exceed about 10 andgenerally will not exceed about 6, exclusive of the carboxyl-basedgroups. Preferably the acidic reactant will have at least one ethyleniclinkage in an alpha, beta-position with respect to at least one carboxylfunction. Exemplary acidic reactants are acrylic acid, maleic acid,maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,citraconic acid, citraconic anhydride, mesaconic acid, chloromaleicacid, aconitic acid, and the like. Preferred acid reactants includemaleic acid and maleic anhydride.

The ethylenically unsaturated hydrocarbon reactant and the chlorinatedhydrocarbon reactant used in the preparation of these high-molecularweight carboxylic acids (A)(I) are preferably high molecular weight,substantially saturated petroleum fractions and substantially saturatedolefin polymers and the corresponding chlorinated products. Polymers andchlorinated polymers derived from mono-olefins having from 2 to about 30carbon atoms are preferred. Especially useful polymers are the polymersof 1-mono-olefins such as ethylene, propene, 1-butene, isobutene,1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene, and2-methyl-5-propyl-1-hexene. Polymers of medial olefins, i.e., olefins inwhich the olefinic linkage is not at the terminal position, likewise areuseful. These are exemplified by 2-butene, 3-pentene, and 4-octene.

Interpolymers of 1-mono-olefins such as illustrated above with eachother and with other interpolymerizable olefinic substances such asaromatic olefins, cyclic olefins, and polyolefins, are also usefulsources of the ethylenically unsaturated reactant. Such interpolymersinclude for example, those prepared by polymerizing isobutene withstyrene, isobutene with butadiene, propene with isoprene, propene withisobutene, ethylene with piperylene, isobutene with chloroprene,isobutene with p-methyl-styrene, 1-hexene with 1,3-hexadiene, 1-octenewith 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with1-octene, 3,3-dimethyl-1-pentene with 1-hexene, isobutene with styreneand piperylene, etc.

For reasons of hydrocarbon solubility, the interpolymers contemplatedfor use in preparing the acylating agents of this invention arepreferably substantially aliphatic and substantially saturated, that is,they should contain at least about 80% and preferably about 95%, on aweight basis, of units derived from aliphatic mono-olefins. Preferably,they will contain no more than about 5% olefinic linkages based on thetotal number of the carbon-to-carbon covalent linkages present.

In one embodiment of the invention, the polymers and chlorinatedpolymers are obtained by the polymerization of a C₄ refinery streamhaving a butene content of about 35% to about 75% by weight and anisobutene content of about 30% to about 60% by weight in the presence ofa Lewis acid catalyst such as aluminum chloride or boron trifluoride.These polyisobutenes preferably contain predominantly (that is, greaterthan about 80% of the total repeat units) isobutene repeat units of theconfiguration. ##STR2##

The chlorinated hydrocarbons and ethylenically unsaturated hydrocarbonsused in the preparation of the higher molecular weight carboxylicacylating agents preferably have up to about 500 carbon atoms permolecule. Preferred acids (A)(I) are those containing hydrocarbyl groupsof from about 20 to about 500 carbon atoms, more preferably from about30 to about 500 carbon atoms, more preferably from about 40 to about 500carbon atoms, more preferably from about 50 to about 500 carbon atoms.

The high-molecular weight polycarboxylic acids (A)(I) may also beprepared by halogenating a high molecular weight hydrocarbon such as theabove-described olefin polymers to produce a polyhalogenated product,converting the polyhalogenated product to a polynitrile, and thenhydrolyzing the polynitrile. They may be prepared by oxidation of a highmolecular weight polyhydric alcohol with potassium permanganate, nitricacid, or a similar oxidizing agent. Another method involves the reactionof an olefin or a polar-substituted hydrocarbon such as achloropolyisobutene with an unsaturated polycarboxylic acid such as2-pentene-1,3,5-tricarboxylic acid prepared by dehydration of citricacid.

The high-molecular weight acids (A)(I) can also be obtained by reactingchlorinated carboxylic acids, anhydrides, acyl halides, and the likewith ethylenically unsaturated hydrocarbons or ethylenically unsaturatedsubstituted hydrocarbons such as the polyolefins and substitutedpolyolefins described hereinbefore in the manner described in U.S. Pat.No. 3,340,281, this patent being incorporated herein by reference.

The high-molecular weight carboxylic acid anhydrides (A)(I) can beobtained by dehydrating the corresponding acids. Dehydration is readilyaccomplished by heating the acid to a temperature above about 70° C.,preferably in the presence of a dehydration agent, e.g., aceticanhydride. Cyclic anhydrides are usually obtained from polycarboxylicacids having acid groups separated by no more than three carbon atomssuch as substituted succinic or glutaric acid, whereas linear anhydridesare usually obtained from polycarboxylic acids having the acid groupsseparated by four or more carbon atoms.

The acid halides of the mono- and polycarboxylic acids can be preparedby the reaction of the acids or their anhydrides with a halogenatingagent such as phosphorus tribromide, phosphorus pentachloride, orthionyl chloride.

Hydrocarbyl-substituted succinic acids and acid-producing derivativesthereof are particularly preferred as component (A)(I). These acids orderivatives are preferably prepared by reacting maleic anhydride with ahigh molecular weight olefin or a chlorinated hydrocarbon such as achlorinated polyolefin. The reaction involves merely heating the tworeactants at a temperature in the range of about 100° C. to about 300°C., preferably, about 100° C. to about 200° C. The product from thisreaction is a hydrocarbyl-substituted succinic anhydride wherein thesubstituent is derived from the olefin or chlorinated hydrocarbon. Theproduct may be hydrogenated to remove all or a portion of anyethylenically unsaturated covalent linkages by standard hydrogenationprocedures, if desired. The hydrocarbyl-substituted succinic anhydridesmay be hydrolyzed by treatment with water or steam to the correspondingacid and either the anhydride or the acid may be converted to thecorresponding acid halide or ester by reacting with a phosphorus halide,phenol or alcohol. The hydrocarbyl-substituted succinic acids andanhydrides (A)(I) can be represented by the formulae ##STR3## wherein Ris the hydrocarbyl substituent. Preferably R contains from about 20 toabout 500 carbon atoms, more preferably from about 30 to about 500carbon atoms, more preferably from about 40 to about 500 carbon atoms,more preferably from about 50 to about 500 carbon atoms.

Although it is preferred that component (A)(I) is an aliphatic mono- orpolycarboxylic acid, and more preferably a dicarboxylic acid, thecarboxylic acid (A)(I) may also be an aromatic mono- or polycarboxylicacid or acid-producing compound. The aromatic acids are preferablyalkyl-substituted, mono- or dicarboxy-substituted benzene, naphthalene,anthracene, phenanthrene or like aromatic hydrocarbons. The alkyl groupsmay contain up to about 30 carbon atoms. The aromatic acid may alsocontain other substituents such as halo, hydroxy, lower alkoxy, etc.

The Alcohols Useful In Making the Hydrocarbyl-Substituted CarboxylicAcid Ester Derivatives (A)(I) and (B)(I):

The alcohols useful in making the hydrocarbyl-substituted carboxylicacid ester derivatives (A)(I) and (B)(I) of this invention include thosecompounds of the general formula:

    R.sub.1 --(OH).sub.m

wherein R₁ is a monovalent or polyvalent organic group joined to the--OH groups through carbon-to-oxygen bonds (that is, --COH wherein thecarbon is not part of a carbonyl group) and m is an integer of from 1 toabout 10, preferably 2 to about 6. These alcohols can be aliphatic,cycloaliphatic, aromatic, and heterocyclic, includingaliphatic-substituted cycloaliphatic alcohols, aliphatic-substitutedaromatic alcohols, aliphatic-substituted heterocyclic alcohols,cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted heterocyclic alcohols,heterocyclic-substituted aliphatic alcohols, heterocyclic-substitutedcycloaliphatic alcohols, and heterocyclic-substituted aromatic alcohols.Except for the polyoxyalkylene alcohols, the mono- and polyhydricalcohols corresponding to the formula R₁ --(OH)_(m) preferably containnot more than about 40 carbon atoms, more preferably not more than about20 carbon atoms. The alcohols may contain nonhydrocarbon substituents orgroups which do not interfere with the reaction of the alcohols with thehydrocarbyl-substituted carboxylic acids or anhydrides of thisinvention. Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., -- as in such groups as --CH₂ CH₂ --X--CH₂ CH₂ --where X is --O-- or --S--).

Among the polyoxyalkylene alcohols suitable for use in the preparationof the ester derivatives of this invention are the commerciallyavailable polyoxyalkylene alcohols that include the polyoxyethylatedamines, amides, and quaternary salts available from Armour IndustrialChemical Co. under the names ETHODUOMEEN polyethoxylatedhigh-molecular-weight aliphatic diamines; ETHOMEEN, polyethoxylatedaliphatic amines containing alkyl groups in the range of about 8 toabout 18 carbon atoms; ETHOMID, polyethoxylated high-molecular weightamides; and ETHOQUAD, polyethoxylated quaternary ammonium chloridesderived from long-chain amines.

Useful polyoxyalkylene alcohols and derivatives thereof include thehydrocarbyl ethers and the carboxylic acid esters obtained by reactingthe alcohols with various carboxylic acids. Illustrative hydrocarbylgroups are alkyl, cycloalkyl, alkylaryl, aralkyl, alkylaryl alkyl, etc.,containing up to about 40 carbon atoms. Specific hydrocarbyl groupsinclude methyl, butyl, dodecyl, tolyl, phenyl, naphthyl, dodecylphenyl,p-octylphenyl ethyl, cyclohexyl, and the like. Carboxylic acids usefulin preparing the ester derivatives are mono- or polycarboxylic acidssuch as acetic acid, valeric acid, lauric acid, stearic acid, succinicacid, and alkyl or alkenyl-substituted succinic acids wherein the alkylor alkenyl group contains up to about 20 carbon atoms. Members of thisclass of alcohols are commercially available from various sources; e.g.,PLURONICS, polyols available from Wyandotte Chemicals Corporation;POLYGLYCOL 112-2, a liquid triol derived from ethyleneoxide andpropylene-oxide available from Dow Chemical Co.; and TERGITOLS,dodecylphenyl or nonylphenyl polyethylene glycol ethers, and UCONS,polyalkylene glycols and various derivatives thereof, both availablefrom Union Carbide Corporation. However, the alcohols used must have anaverage of at least one free alcoholic hydroxyl group per molecule ofpolyoxyalkylene alcohol. For purposes of describing thesepolyoxyalkylene alcohols, an alcoholic hydroxyl group is one attached toa carbon atom that does not form part of an aromatic nucleus.

Alcohols useful in this invention also include alkylene glycols andpolyoxyalkylene alcohols such as polyoxyethylene alcohols,polyoxypropylene alcohols, polyoxybutylene alcohols, and the like. Thesepolyoxyalkylene alcohols (sometimes called polyglycols) can contain upto about 150 oxyalkylene groups, with the alkylene group containing fromabout 2 to about 8 carbon atoms. Such polyoxyalkylene alcohols aregenerally dihydric alcohols. That is, each end of the moleculeterminates with an OH group. In order for such polyoxyalkylene alcoholsto be useful, there must be at least one such OH group. However, theremaining OH group can be esterified with a monobasic, aliphatic oraromatic carboxylic acid of up to about 20 carbon atoms such as aceticacid, propionic acid, oleic acid, stearic acid, benzoic acid, and thelike. The monoethers of these alkylene glycols and polyoxyalkyleneglycols are also useful. These include the monoaryl ethers, monoalkylethers, and monoaralkyl ethers of these alkylene glycols andpolyoxyalkylene glycols. This group of alcohols can be represented bythe formula

    HO--(--R.sub.A O--).sub.p R.sub.B --OR.sub.C

wherein R_(A) and R_(B) are independently alkylene groups of from about2 to 8 carbon atoms; and R_(C) is aryl (e.g., phenyl), lower alkoxyphenyl, or lower alkyl phenyl, or lower alkyl (e.g., ethyl, propyl,terbutyl, pentyl, etc.); and aralkyl (e.g., benzyl, phenylethyl,phenylpropyl, p-ethylphenylethyl, etc.); p is from zero to about eight,preferably from about 2 to 4. Polyoxyalkylene glycols where the alkylenegroups are ethylene or propylene and p is at least two as well as themonoethers thereof as described above are useful.

The monohydric and polyhydric alcohols useful in this invention includemonohydroxy and polyhydroxy aromatic compounds. Monohydric andpolyhydric phenols and naphthols are preferred hydroxyaromaticcompounds. These hydroxy-substituted aromatic compounds may containother substituents in addition to the hydroxy substituents such as halo,alkyl, alkenyl, alkoxy, alkylmercapto, nitro and the like. Usually, thehydroxy aromatic compound will contain from 1 to about 4 hydroxy groups.The aromatic hydroxy compounds are illustrated by the following specificexamples: phenol, p-chlorophenol, p-nitrophenol, beta-naphthol,alpha-naphthol, cresols, resorcinol, catechol, carvacrol, thymol,eugenol, p,p'-dihydroxy-biphenyl, hydroquinone, pyrogallol,phloroglucinol, hexylresorcinol, orcin, quaiacol, 2-chlorophenol,2,4-dibutylphenol, propenetetramer-substituted phenol, didodecylphenol,4,4'-methylene-bis-methylene-bis-phenol, alpha-decyl-beta-naphthol,polyisobutenyl-(molecular weight of about 1000)-substituted phenol, thecondensation product of heptylphenol with about 0.5 mole offormaldehyde, the condensation product of octylphenol with acetone,di(hydroxyphenyl)oxide, di-(hydroxyphenyl)sulfide,di(hydroxyphenyl)-disulfide, and 4-cyclohexylphenol. Phenol itself andaliphatic hydrocarbon-substituted phenols, e.g., alkylated phenolshaving up to 3 aliphatic hydrocarbon substituents are useful. Each ofthe aliphatic hydrocarbon substituents may contain about 100 or morecarbon atoms but usually will have from 1 to about 20 carbon atoms.Alkyl and alkenyl groups are the preferred aliphatic hydrocarbonsubstituents.

Further specific examples of monohydric alcohols which can be usedinclude monohydric alcohols such as methanol, ethanol, isooctanol,dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol,hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol,beta-phenylethyl alcohol, 2-methylcyclohexanol, beta-chloroethanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, sec-pentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol,nitro-octadecanol, and dioleate of glycerol. Alcohols useful in thisinvention may be unsaturated alcohols such as allyl alcohol, cinnamylalcohol, 1-cyclohexene-3-ol and oleyl alcohol.

Other specific alcohols useful in this invention are the ether alcoholsand amino alcohols including, for example, the oxyalkylene-,oxyarylene-, amino-alkylene-, and amino-arylene-substituted alcoholshaving one or more oxyalkylene, aminoalkylene oramino-arylene-oxy-arylene groups. These alcohols are exemplified by theCellosolves, (products of Union Carbide identified as mono- and dialkylethers of ethylene glycol and their derivatives), the Carbitols(products of Union Carbide identified as mono- and dialkyl ethers ofdiethylene glycol and their derivatives), phenoxyethanol,heptylphenyl-(oxypropylene)₆ -OH, octyl-(oxyethylene)₃₀ -OH,phenyl-(oxyoctylene)₂ -OH, mono-(heptylphenyloxypropylene)-substitutedglycerol, poly(styreneoxide), aminoethanol, 3-aminoethylpentanol,di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylenediamine,N,N,N',N'-tetrahydroxytrimethylenediamine, and the like.

The polyhydric alcohols preferably contain from 2 to about 10 hydroxygroups. They are illustrated, for example, by the alkylene glycols andpolyoxyalkylene glycols mentioned above such as ethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tripropylene glycol, dibutylene glycol, tributylene glycol, andother alkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain from 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used. Thecarbohydrates may be exemplified by glucose, fructose, sucrose, rhamose,mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not allof which have been esterified with an aliphatic monocarboxylic acidhaving from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful. Further specific examples of such partially esterifiedpolyhydric alcohols are the monooleate of sorbitol, distearate ofsorbitol, monooleate of glycerol, monostearate of glycerol,di-dodecanoate of erythritol, and the like.

Useful alcohols also include those polyhydric alcohols containing up toabout 12 carbon atoms, and especially those containing from about 3 toabout 10 carbon atoms. This class of alcohols includes glycerol,erythritol, pentaerythritol, dipentaerythritol, gluconic acid,glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol,1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol,2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis-(hydroxymethyl)cyclohexanol, 1,10-decanediol,digitalose, and the like. Aliphatic alcohols containing at least about 3hydroxyl groups and up to about 10 carbon atoms are useful.

Useful polyhydric alcohols are the polyhydric alkanols containing fromabout 3 to about 10 carbon atoms and particularly, those containingabout 3 to about 6 carbon atoms and having at least three hydroxylgroups. Such alcohols are exemplified by glycerol, erythritol,pentaerythritol, mannitol, sorbitol,2-hydroxymethyl-2-methyl-1,3-propanediol-(trimethylolethane),2-hydroxymethyl-2-ethyl-1,3-propanediol(trimethylopropane),1,2,4-hexanetriol, and the like.

The carboxylic acids or anhydrides can be reacted with the alcoholsaccording to conventional esterification techniques to form the esterderivatives (A)(I) and (B)(I). This normally involves heating the acidor anhydride with the alcohol, optionally in the presence of a normallyliquid, substantially inert, organic liquid solvent/diluent and/or inthe presence of esterification catalyst. Temperatures of at least about30° C. up to the decomposition temperature of the reaction componentand/or product having the lowest such temperature can be used. Thistemperature is preferably in the range of about 50° C. to about 130° C.,more preferably about 80° C. to about 100° C. when a carboxylicanhydride is used as the carboxylic reactant. On the other hand, whenthe carboxylic reactant is an acid, the temperature is preferably in therange of about 100° C. up to about 300° C. with temperatures of about140° C. to 250° C. often being employed. Usually, about 0.05 to about0.95 equivalent of alcohol are used for each equivalent of acid oranhydride. Preferably, about 0.5 equivalent of alcohol per equivalent ofacid or anhydride is employed. An equivalent an of alcohol is itsmolecular weight divided by the total number of hydroxyl groups presentin the molecule. Thus, an equivalent weight of ethanol is its molecularweight while the equivalent weight of ethylene glycol is one-half itsmolecular weight. The number of equivalents of the acid or anhydridedepends on the total number of carboxylic functions (e.g., carboxylicacid or carboxylic anhydride groups) present in the acid or anhydride.Thus, the number of equivalents of the acid or anhydride will vary withthe number of carboxy groups present therein. In determining the numberof equivalents of the acid or anhydride, those carboxyl functions whichare not capable of reacting as a carboxylic acid acylating agent areexcluded. In general, however, there is one equivalent of acid oranhydride for each carboxy group in the acid or anhydride. For example,there would be two equivalents in an anhydride derived from the reactionof one mole of olefin polymer and one mole of maleic anhydride.Conventional techniques are readily available for determining the numberof carboxyl functions (e.g., acid number, saponification number) and,thus, the number of equivalents of acid or anhydride available to reactwith the alcohol can be readily determined by one skilled in the art.

Many issued patents disclose procedures for reacting carboxylic acids oracid-producing compounds with alcohols to produce acidic esters andneutral esters. These same techniques are applicable to preparing estersfrom the hydrocarbyl-substituted carboxylic acids and/or anhydridesthereof of this invention and the alcohols described above. All that isrequired is that the acid and/or anhydride, of this invention issubstituted for the carboxylic acids or acid-producing compoundsdiscussed in these patents, usually on an equivalent weight basis. Thefollowing U.S. patents are expressly incorporated herein by referencesfor their disclosure of suitable methods for reacting the acids and/oranhydrides of this invention with the alcohols described above: U.S.Pat. Nos. 3,331,776; 3,381,022; 3,522,179; 3,542,680; 3,697,428; and3,755,169.

The Amines Useful In Making the Amide Derivatives (A)(I) and (B)(I)

The amines useful in making the hydrocarbyl-substituted carboxylic acidamide derivatives (A)(I) and (B)(I) include ammonia, primary amines andsecondary amines, with the secondary amines being preferred. Theseamines are characterized .by the presence within their structure of atleast one H-N<group and/or at least one --NH₂ group. These amines can bemonoamines or polyamines. Hydrazine and substituted hydrazinescontaining up to three substituents are included as amines suitable forpreparing the derivatives (A)(I) and (B)(I). Mixtures of two or moreamines can be used.

The amines can be aliphatic, cycloaliphatic, aromatic or heterocyclic,including aliphatic-substituted aromatic, aliphatic-substitutedcycloaliphatic, aliphatic-substituted heterocyclic,cycloaliphatic-substituted aliphatic, cycloaliphatic-substitutedaromatic, cycloaliphatic-substituted heterocyclic, aromatic-substitutedaliphatic, aromatic-substituted cycloaliphatic, aromatic-substitutedheterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted cycloaliphatic and heterocyclic-substitutedaromatic amines. These amines may be saturated or unsaturated. Ifunsaturated, the amine is preferably free from aceylenic unsaturation.The amines may also contain non-hydrocarbon substituents or groups aslong as these groups do not significantly interfere with the reaction ofthe amines with the hydrocarbyl-substituted carboxylic acids andderivatives thereof of this invention. Such non-hydrocarbon substituentsor groups include lower alkoxy, lower alkyl, mercatto, nitro, andinterrupting groups such as --O-- and --S-- (e.g., as in such groups as--CH₂ CH₂ --X--CH₂ CH₂ -- where X is --O-- or --S--).

With the exception of the branched polyalkylene polyamines, thepolyoxyalkylene polyamines and the high molecular weighthydrocarbyl-substituted amines described more fully hereinafter, theamines used in this invention ordinarily contain less than about 40carbon atoms in total and usually not more than about 20 carbon atoms intotal.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substitutedamines wherein the aliphatic groups can be saturated or unsaturated andstraight or branched chain. Thus, they are primary or secondaryaliphatic amines. Such amines include, for example, mono- anddi-alkyl-substituted amines, mono- and di-alkenyl-substituted amines,and amines having one N-alkenyl substituent and one N-alkyl substituent,and the like. The total number of carbon atoms in these aliphaticmonoamines preferably does not exceed about 40 and usually does notexceed about 20 carbon atoms. Specific examples of such monoaminesinclude ethylamine, di-ethylamine, n-butylamine, di-n-butylamine,allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,octadecylamine, and the like. Examples of cycloaliphatic-substitutedaliphatic amines, aromatic-substituted aliphatic amines, andheterocyclic-substituted aliphatic amines, include2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and3-(furylpropyl) amine.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines, N-ethyl-cyclohexylamines,dicyclohexylamines, and the like. Examples of aliphatic-substituted,aromatic-substituted, and heterocyclic-substituted cycloaliphaticmonoamines include propyl-substituted cyclohexylamines,phenyl-substituted cyclopentylamines and pyranyl-substitutedcyclohexylamine.

Suitable aromatic amines include those monoamines wherein a carbon atomof the aromatic ring structure is attached directly to the aminonitrogen. The aromatic ring will usually be a mononuclear aromatic ring(i.e., one derived from benzene) but can include fused aromatic rings,especially those derived from naphthylene. Examples of aromaticmonoamines include aniline, di(para-methylphenyl) amine, naphthylamine,N-(n-butyl) aniline, and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines include para-ethoxyaniline, paradodecylamine,cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Suitable polyamines include aliphatic, cycloaliphatic and aromaticpolyamines analogous to the above-described monoamines except for thepresence within their structure of another amino nitrogen. The otheramino nitrogen can be a primary, secondary or tertiary amino nitrogen.Examples of such polyamines include N-aminopropyl-cyclohexylamine,N-N'-di-n-butyl-para-phenylene diamine, bis-(para-aminophenyl)-methane,1,4-diaminocyclohexane, and the like.

Heterocyclic mono- and polyamines can also be used in making thehydrocarbyl-substituted carboxylic acid amide derivatives (A)(I) and(B)(I). As used herein, the terminology "heterocyclic mono- andpolyamine(s)" is intended to describe those heterocyclic aminescontaining at least one primary or secondary amino group and at leastone nitrogen as a heteroatom in the heterocyclic ring. However, as longas there is present in the heterocyclic mono- and polyamines at leastone primary or secondary amino group, the hetero-N atom in the ring canbe a tertiary amino nitrogen; that is, one that does not have hydrogenattached directly to the ring nitrogen. Heterocyclic amines can besaturated or unsaturated and can contain various substituents such asnitro, alkoxy, alkyl mercapto, alkyl, alkenyl, aryl, alkaryl, or aralkylsubstituents. Generally, the total number of carbon atoms in thesubstituents will not exceed about 20. Heterocyclic amines can containheteroatoms other than nitrogen, especially oxygen and sulfur. Obviouslythey can contain more than one nitrogen heteroatom. The 5- and6-membered heterocyclic rings are preferred.

Among the suitable heterocyclics are aziridines, azetidines, azolidines,tetra- and di-hydro pyridines, pyrroles, indoles, piperadines,imidazoles, di- and tetra-hydroimidazoles, piperazines, isoindoles,purines, morpholines, thiomorpholines, N-aminoalkyl-morpholines,N-aminoalkylthiomorpholines, N-aminoalkyl-piperazines,N,N'-di-aminoalkylpiperazines, azepines, azocines, azonines, azecinesand tetra-, di- and perhydro derivatives of each of the above andmixtures of two or more of these heterocyclic amines. Preferredheterocyclic amines are the saturated 5- and 6-membered heterocyclicamines containing only nitrogen, oxygen and/or sulfur in the heteroring, especially the piperidines, piperazines, thiomorpholines,morpholines, pyrrolidines, and the like. Piperidine,aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substitutedpiperazines, morpholine, aminoalkyl-substituted morpholines,pyrrolidine, and aminoalkyl-substituted pyrrolidines, are useful.Usually the aminoalkyl substituents are substituted on a nitrogen atomforming part of the hetero ring. Specific examples of such heterocyclicamines include N-aminopropylmorpholine, N-aminoethylpiperazine, andN,N'-di-aminoethyl-piperazine.

Hydroxyamines both mono- and polyamines, analogous to those describedabove are also useful provided they contain at least one primary orsecondary amino group. Hydroxy-substituted amines having only tertiaryamino nitrogens, such as in trihydroxyethyl amine, are thus excluded asamines, but can be used as alcohols as disclosed above. Thehydroxy-substituted amines contemplated are those having hydroxysubstituents bonded directly to a carbon atom other than a carbonylcarbon atom; that is, they have hydroxy groups capable of functioning asalcohols. Examples of such hydroxy-substituted amines includeethanolamine, di(3-hydroxypropyl)amine, 3-hydroxybutylamine,4-hydroxybutylamine, diethanolamine, di(2-hydroxypropyl) amine,N-hydroxypropyl propylamine, N-(2-hydroxyethyl)-cyclohexylamine,3-hydroxycyclopentylamine, para-hydroxyaniline, N-hydroxyethylpiperazine, and the like.

Also suitable as amines are the aminosulfonic acids and derivativesthereof corresponding to the formula: ##STR4## wherein R is OH, NH₂,ONH₄, etc.; R_(a) is a polyvalent organic group having a valence equalto x+y; R_(b) and R_(c) are each independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl with the proviso that at least one of R_(b) andR_(c) is hydrogen per aminosulfonic acid molecule; x and y are eachintegers equal to or greater than one. Each aminosulfonic reactant ischaracterized by at least one HN< or H₂ N-- group and at least one##STR5## group. These sulfonic acids can be aliphatic, cycloaliphatic oraromatic aminosulfonic acids and the corresponding functionalderivatives of the sulfo group. Specifically, the aminosulfonic acidscan be aromatic aminosulfonic acids, that is, where R_(a) is apolyvalent aromatic group such as phenylene where at least one ##STR6##group is attached directly to a nuclear carbon atom of the aromaticgroup. The aminosulfonic acid may also be a mono-amino aliphaticsulfonic acid; that is, an acid where x is one and R_(a) is a polyvalentaliphatic group such as ethylene, propylene, trimethylene, and2-methylene propylene. Other suitable aminosulfonic acids andderivatives thereof useful as amines in this invention are disclosed inU.S. Pat. Nos. 3,029,250; 3,367,864; and 3,926,820; which areincorporated herein by reference.

Hydrazine and substituted-hydrazine can also be used as amines in thisinvention. At least one of the nitrogens in the hydrazine must contain ahydrogen directly bonded thereto. The substituents which may be presenton the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and thelike. Usually the substituents are alkyl, especially lower alkyl,phenyl, and substituted phenyl such as lower alkoxy-substituted phenylor lower alkyl-substituted phenyl. Specific examples of substitutedhydrazines are methylhydrazine, N,N-dimethylhydrazine,N,N'-dimethylhydrazine, phenylhydrazine, N-phenyl-N'-ethylhydrazine,N-(para-tolyl)-N'-(n-butyl)-hydrazine, N-(para-nitrophenyl)-hydrazine,N-(para-nitrophenyl)-N-methylhydrazine,N,N'-di-(parachlorophenol)-hydrazine, N-phenyl-N'-cyclohexylhydrazine,and the like.

The high molecular weight hydrocarbyl amines, both monoamines andpolyamines, which can be used as amines in this invention are generallyprepared by reacting a chlorinated polyolefin having a molecular weightof at least about 400 with ammonia or an amine. The amines that can beused are known in the art and described, for example, in U.S. Pat. Nos.3,275,554 and 3,438,757, both of which are incorporated herein byreference. These amines must possess at least one primary or secondaryamino group.

Another group of amines suitable for use in this invention are branchedpolyalkylene polyamines. The branched polyalkylene polyamines arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylene##STR7## group per nine amino units present on the main chain; forexample, 1-4 of such branched chains per nine units on the main chain,but preferably one side chain unit per nine main chain units. Thus,these polyamines contain at least three primary amino groups and atleast one tertiary amino group. These amines may be expressed by theformula: ##STR8## wherein R is an alkylene group such as ethylene,propylene, butylene and other homologs (both straight chained andbranched), etc., but preferably ethylene; and x, y and z are integers; xis in the range of from about 4 to about 24 or more, preferably fromabout 6 to about 18; y is in the range of from 1 to about 6 or more,preferably from 1 to about 3; and z is in the range of from zero toabout 6, preferably from zero to about 1. The x and y units may besequential, alternative, orderly or randomly distributed. A useful classof such polyamines includes those of the formula: ##STR9## wherein n isan integer in the range of from 1 to about 20 or more, preferably in therange of from 1 to about 3, and R is preferably ethylene, but may bepropylene, butylene, etc. (straight chained or branched). Usefulembodiments are represented by the formula: ##STR10## wherein n is aninteger in the range of 1 to about 3. The groups within the brackets maybe joined in a head-to-head or a head-to-tail fashion. U.S. Pat. Nos.3,200,106 and 3,259,578 are incorporated herein by reference for theirdisclosures relative to said polyamines.

Suitable amines also include polyoxyalkylene polyamines, e.g.,polyoxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to about 4000, preferably fromabout 400 to 2000. Examples of these polyoxyalkylene polyamines includethose amines represented by the formula:

    NH.sub.2 --Alkylene--O--Alkylene).sub.m NH.sub.2

wherein m has a value of from about 3 to about 70, preferably from about10 to about 35; and the formula:

    R--[Alkylene--O--Alkylene).sub.n NH.sub.2 ].sub.3-6

wherein n is a number in the range of from 1 to about 40, with theproviso that the sum of all of the n's is from about 3 to about 70 andgenerally from about 6 to about 35, and R is a polyvalent saturatedhydrocarbyl group of up to about 10 carbon atoms having a valence offrom about 3 to about 6. The alkylene groups may be straight or branchedchains and contain from 1 to about 7 carbon atoms, and usually from 1 toabout 4 carbon atoms. The various alkylene groups present within theabove formulae may be the same or different.

More specific examples of these polyamines include: ##STR11## wherein xhas a value of from about 3 to about 70, preferably from about 10 to 35;and ##STR12## wherein x+y+z have a total value ranging from about 3 toabout 30, preferably from about 5 to about 10.

Useful polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to about 2000. Thepolyoxyalkylene polyamines are commercially available from the JeffersonChemical Company, Inc. under the trade name "Jeffamine". U.S. Pat. Nos.3,804,763 and 3,948,800 are incorporated herein by reference for theirdisclosure of such polyoxyalkylene polyamines.

Useful amines are the alkylene polyamines, including the polyalkylenepolyamines, as described in more detail hereafter. The alkylenepolyamines include those conforming to the formula: ##STR13## wherein nis from 1 to about 10; each R is independently a hydrogen atom, ahydrocarbyl group or a hydroxy-substituted hydrocarbyl group having upto about 700 carbon atoms, preferably up to about 100 carbon atoms, morepreferably up to about 30 carbon atoms; and the "Alkylene" group hasfrom about 1 to about 10 carbon atoms with the preferred alkylene beingethylene or propylene. Useful are the alkylene polyamines wherein each Ris hydrogen with the ethylene polyamines, and mixtures of ethylenepolyamines being particularly preferred. Usually n will have an averagevalue of from about 2 to about 7. Such alkylene polyamines includemethylene polyamines, ethylene polyamines, butylene polyamines,propylene polyamines, pentylene polamines, hexylene polyamines,heptylene polyamines, etc. The higher homologs of such amines andrelated aminoalkyl-substituted piperazines are also included.

Alkylene polyamines that are useful include ethylene diamine,triethylene tetramine, propylene diamine, trimethylene diamine,hexamethylene diamine, decamethylene diamine, octamethylene diamine,di(heptamethylene) triamine, tripropylene tetramine, tetraethylenepentamine, trimethylene diamine, pentaethylene hexamine,di(trimethylene) triamine, N-(2-aminoethyl) piperazine,1,4-bis(2-aminoethyl) piperazine, and the like. Higher homologs as areobtained by condensing two or more of the above-illustrated alkyleneamines are useful as amines in this invention as are mixtures of two ormore of any of the afore-described polyamines.

Ethylene polyamines, such as those mentioned above, are described indetail under the heading "Diamines and Higher Amines" in TheEncyclopedia of Chemical Technology, Second Edition, Kirk and Othmer,Volume 7, pages 27-39, Interscience Publishers, Division of John Wileyand Sons, 1965, these pages being incorporated herein by reference. Suchcompounds are prepared most conveniently by the reaction of an alkylenechloride with ammonia or by reaction of an ethylene imine with aring-opening reagent such as ammonia, etc. These reactions result in theproduction of the somewhat complex mixtures of alkylene polyamines,including cyclic condensation products such as piperazines.

To prepare the hydrocarbyl-substituted carboxylic acid amide derivatives(A)(I) and (B)(I), one or more of the acid or anhydride and one or moreof ammonia or the above-described primary or secondary amines are mixedtogether and heated, optionally in the presence of a normally liquid,substantially inert organic liquid solvent/diluent, at temperatures ofabout 30° C. of to the decomposition temperature of the reactioncomponent and/or product having the lowest such temperature. Thistemperature is preferably in the range of about 50° C. to about 130° C.,more preferably about 80° C. to about 100° C. when the carboxylicreactant is an anhydride. On the other hand, when the carboxylicreactant is an acid, the temperature is preferably in the range of about100° C. to about 300° C., more preferably from about 125° C. to about250° C. The acid or anhydride and the ammonia are preferably reacted inamounts sufficient to provide from about 0.05 to about 0.95, preferablyabout 0.5 mole of ammonia per equivalent of acid or anhydride. The acidor anhydride and the amine are preferably reacted in amounts sufficientto provide from about 0.05 to about 0.95, preferably about 0.5equivalent of amine per equivalent of the acid or anhydride. Forpurposes of this reaction, an equivalent of an amine is its molecularweight divided by the total number of >NH and --NH₂ groups present inthe molecule. Thus, ethylene diamine has an equivalent weight equal toone-half its molecular weight; and amino guanidine has an equivalentweight equal to one-fourth its molecular weight. An equivalent ammoniais its molecular weight. An equivalent of an acid or anhydride is thesame as discussed above with respect to reaction with alcohols.

Hydroxyamines Useful in Making the Ester and/or Amide Derivatives (A)(I)and (B)(I)

The hydroxyamines can be primary, secondary or tertiary amines. Theterms "hydroxyamine" and "aminoalcohol" describe the same class ofcompounds and, therefore, can be used interchangeably.

Typically, the hydroxyamines are primary, secondary or tertiary alkanolamines or mixtures thereof. Such amines can be represented,respectfully, by the formulae: ##STR14## wherein each R is independentlya hydrocarbyl group of one to about eight carbon atoms orhydroxyl-substituted hydrocarbyl group of two to about eight carbonatoms and R' is a divalent hydrocarbyl group of about two to about 18carbon atoms. The group --R'--OH in such formulae represents thehydroxyl-substituted hydrocarbyl group. R' can be an acyclic, alicyclicor aromatic group. Typically, R' is an acyclic straight or branchedalkylene group such as an ethylene, 1,2-propylene, 1,2-butylene,1,2-octadecylene, etc. group. Where two R groups are present in the samemolecule they can be joined by a direct carbon-to-carbon bond or througha heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or8-membered ring structure. Examples of such heterocyclic amines includeN-(hydroxyl lower alkyl)-morpholines, -thiomorpholines, -piperidines,-oxazolidines, -thiazolidines and the like. Typically, however, each Ris a lower alkyl group of up to seven carbon atoms.

The hydroxyamines can also be ether N-(hydroxy-substitutedhydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described hydroxy amines (these analogs alsoinclude hydroxyl-substituted oxyalkylene analogs). SuchN-(hydroxyl-substituted hydrocarbyl) amines can be conveniently preparedby reaction of epoxides with afore-described amines and can berepresented by the formulae: ##STR15## wherein x is a number from about2 to about 15 and R and R' are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also beused. Such polyamines can be made by reacting alkylene amines (e.g.,ethylenediamine) with one or more alkylene oxides (e.g., ethylene oxide,octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the afore-described primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid mono- orpolyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl) amines includemono-, di-, and triethanolamine, dimethylethanolamine,diethylethanolamine, di-(3-hydroxylpropyl) amine, N-(3-hydroxylbutyl)amine, N-(4-hydroxylbutyl) amine, N,N-di-(2-hydroxylpropyl) amine,N-(2-hydroxylethyl) morpholine and its thio analog, N-(2-hydroxylethyl)cyclohexylamine, N-3-hydroxyl cyclopentylamine, o-, m- andp-aminophenol, N-(hydroxylethyl) piperazine, N,N'-di(hydroxylethyl)piperazine, and the like.

Further hydroxyamines are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula

    R.sub.a --NH.sub.2

wherein R_(a) is a monovalent organic group containing at least onealcoholic hydroxy group. The total number of carbon atoms in R_(a)preferably does not exceed about 20. Hydroxy-substituted aliphaticprimary amines containing a total of up to about 10 carbon atoms areuseful. The polyhydroxy-substituted alkanol primary amines wherein thereis only one amino group present (i.e., a primary amino group) having onealkyl substituent containing up to about 10 carbon atoms and up to about6 hydroxyl groups are useful. These alkanol primary amines correspond toR_(a) --NH₂ wherein R_(a) is a mono-O or polyhydroxy-substituted alkylgroup. It is desirable that at least one of the hydroxyl groups be aprimary alcoholic hydroxyl group. Specific examples of thehydroxy-substituted primary amines include 2-amino-1-butanol,2-amino-2-methyl-1-propanol, p-(beta-hydroxyethyl)-aniline,2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N'-(beta-aminoethyl-piperazine,tris-(hydroxymethyl) amino methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine, beta-(beta-hydroxyethoxy)-ethylamine, glucamine, glusoamine,4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according toprocedures known in the art by reacting isopreneoxide with ammonia),N-3-(aminopropyl)-4-(2-hydroxyethyl)-piperadine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)-1,3-diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxy ethoxyethyl)-ethylenediamine, trismethylolaminomethaneand the like. U.S. Pat. No. 3,576,743 is incorporated herein byreference.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful. Usefulhydroxyalkyl-substituted alkylene polyamines include those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropyl-substituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia and condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater.

The hydrocarbyl-substituted carboxylic acids or anhydrides (A)(I) and(B)(I) can be reacted with the hydroxyamine according to conventionalester- and/or amide-forming techniques. This normally involves heatingthe acid or anhydride with the hydroxyamine, optionally in the presenceof a normally liquid, substantially inert, organic liquidsolvent/diluent. Temperatures of at least about 30° C. up to thedecomposition temperature of the reaction component and/or producthaving the lowest such temperature can be used. This temperature ispreferably in the range of about 50° C. to about 130° C., preferablyabout 80° C. to about 100° C. when the carboxylic reactant is ananhydride. On the other hand, when the carboxylic reactant is an acid,this temperature is preferably in the range of about 100° C. up to about300° C. with temperatures in the range of about 125° C. to about 250° C.often being employed. Usually, about 0.05 to about 0.95, preferablyabout 0.5 equivalent of hydroxyamine are used for each equivalent ofacid or anhydride. For purposes of this reaction, an equivalent of ahydroxyamine is its molecular weight divided by the total number of--OH, >NH and --NH₂ groups present in the molecule. Thus,diethylethanolamine has an equivalent weight equal to its molecularweight; ethanolamine has an equivalent weight equal to one-half itsmolecular weight. An equivalent of acid or anhydride is the same asdiscussed above with respect to reaction with alcohols.

Components (A)(II) and (B)(II)

Components (A)(II) and (B)(II) include ammonia all of the primaryamines, secondary amines and hydroxyamines discussed above as beinguseful in preparing the derivatives (A)(I) and (B)(I). In addition toammonia, the amines and hydroxyamines discussed above, component (A)(II)and (B)(II) also include tertiary amines. The term "amine" is usedherein to include hydroxyamines and aminoalcohols. The tertiary aminesare analogous to the primary and secondary amines discussed above withthe exception that hydrogen atoms in the H--N< or --NH₂ groups arereplaced by hydrocarbyl groups. These tertiary amines can be monoaminesor polyamines. The monoamines are represented by the formula ##STR16##wherein R', R² and R³ are the same or different hydrocarbyl groups.Preferably, R', R² and R³ are independently hydrocarbyl groups of from 1to about 20 carbon atoms. The tertiary amines can be symmetrical amines,dimethylalkyl amines or those derived from the reaction of a primaryamine or a secondary amine with ethylene oxide. The tertiary amines canbe aliphatic, cycloaliphatic, aromatic or heterocyclic, includingaliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic,aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic substituted aromatic,cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic,aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substitutedcycloaliphatic and heterocyclic-substituted aromatic ames. Thesetertiary amines may be saturated or unsaturated. If unsaturated, theamine is preferably free from acetylenic unsaturation (i.e., --C═C--).The tertiary amines may also contain non-hydrocarbon substituents orgroups as long as these groups do not significantly interfere with thereaction of the amines with components (A)(I) or (B)(I) of thisinvention. Such non-hydrocarbon substituents or groups include loweralkoxy, lower alkyl, mercapto, nitro, and interrupting groups such as--O-- and --S-- (e.g., as in such groups as --CH₂ CH₂ --X-- CH₂ CH₂ --where X is --O-- or --S--). Examples of such tertiary amines includetrimethyl amine, triethyl amine, tripropyl amine, tributyl amine,monomethyldiethyl amine, monoethyldimethyl amine, dimethylpropyl amine,dimethylbutyl amine, dimethylpentyl amine, dimethylhexyl amine,dimethylheptyl amine, dimethyloctyl amine, dimethylnonyl amine,dimethyldecyl amine, dimethyldicodanyl amdne, dimethylphenyl amine,N,N-dioctyl-1-octanamine, N,N-didodecyl-1-dodecanamine tricoco amine,trihydrogenated-tallow amine, N-methyl-dihydrogenated tallow amine,N,N-dimethyl-1-dodecandmine, N,N-dimethyl-1-tetradecanamine,N,N-dimethyl-1-hexadecanamine, N,N-dimethyl-1-octadecanamine,N,N-dimethylcoco, amine, N,N-dimethyl soyaamine, N,N-dimethylhydrogenated tallow amine, etc.

Useful polyamines include the alkylene polyamines discussed above aswell as alkylene polyamines with no hydrogens attached to the nitrogenatoms. Thus, the alkylene polyamines useful as components (A)(II) and(B)(II) include those conforming to the formula: ##STR17## wherein n isfrom 1 to about 10, preferably from 1 to about 7; each R isindependently a hydrogen atom, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, preferably up to about 100 carbon atoms, more preferably up toabout 50 carbon atoms, more preferably up to about 30 carbon atoms; andthe "Alkylene" group has from about 1 to about 18 carbon atoms,preferably from 1 to about 4 carbon atoms, with the preferred Alkylenebeing ethylene or propylene.

The alkali and alkaline earth metals that are useful as components(A)(II) and (B)(II) can be any alkali or alkaline earth metal. Thealkali metals are preferred. Sodium and potassium are particularlypreferred. The alkali and alkaline earth metal compounds that are usefulinclude, for example, the oxides, hydroxides and carbonates. Sodiumhydroxide and potassium hydroxide are particularly preferred.

Formation of the Salt Compositions (A) and (B)

The salt compositions (A) and (B) of the invention can be prepared byreacting component (A)(I) with component (A)(II), and reacting component(B)(I) with component (B)(II), under salt-forming conditions to form thedesired salt compositions. The ratio of reactants utilized in thepreparation of the salt compositions (A) and (B) may be varied over awide range. Generally, from about 0.1 to about 2 equivalents or more,preferably about 0.5 to about 1.5 equivalents of components (A)(II) and(B)(II) are used for each equivalent of components (A)(I) and (B)(I),respectively.

For purposes of this reaction, an equivalent of components (A)(I) or(B)(I) in the acid or anhydride form is the same as discussed above withrespect to the reaction of the acids and anhydrides with alcohols. Thenumber of equivalents of component (A)(I) or (B)(I) in the ester and/oramide derivative form, depends on the total number of carboxy groupspresent that are capable of reacting as a carboxylic acid acylatingagent; that is the number of carboxy groups present that are capable offorming a carboxylic salt with components (A)(II) and (B)(II),respectively. For example, there would be one equivalent in anacid/amide derived from one mole of a polyisobutylene-substitutedsuccinic anhydride and one mole of ammonia. Similarly, there would beone equivalent in an acid/ester derived from one mole of apolyisobutylene-substituted succinic anhydride and methanol. Whencomponent (A)(II) and/or (B)(II) is an amine, an equivalent thereof isits molecular weight divided by the total number of nitrogens present inthe molecule that are sufficiently basic to form a salt with components(A)(I) and/or (B)(I), respectively. These include, for example, thenitrogen atoms of primary aliphatic amines, secondary aliphatic aminesand tertiary aliphatic amines as well as amines bearing one aryl groupon the nitrogen atom (e.g., aniline). On the other hand, these do notinclude, for example, amides, (i.e., ##STR18## or imides ##STR19## Thus,octylamine has an equivalent weight equal to its molecular weight;ethylene diamine has an equivalent weight equal to one-half of itsmolecular weight; both ethanolamine and diethylethanolamine haveequivalent weights equal to their molecular weights. The equivalentweight of a commercially available mixture of polyalkylene polyaminescan be determined by dividing the atomic weight of nitrogen (14) by the% N contained in the polyamine; thus, a polyalkylene polyamine mixturehaving a % N of 34 would have an equivalent weight of 41.2. Whencomponent (A)(II) and/or (B)(II) is ammonia, an equivalent weightthereof is its molecular weight. When component (A)(II) and/or (B)(II)is an alkali or alkaline earth metal, an equivalent weight thereof isits molecular weight. When component (A)(II) and/or (B)(II) is an alkalior alkaline earth metal compound, an equivalent weight thereof is itsmolecular weight divided by the number of alkali or alkaline earth metalatoms present in the molecule.

The products of the reaction between components (A)(I) and (A)(II), and(B)(I) and (B)(II), respectively, must contain at least some carboxylicsalt in order for said products to be effective as emulsifiers inaccordance with this invention. Thus, these products are typicallyconstituted of compositions containing at least one compound having atleast one carboxylic salt linkage (i.e., ##STR20## wherein M⁺ is analkali or alkaline earth metal, ammonium or amine cation) within itsmolecular structure. This product can also include other compounds suchas amides, esters, and the like. Preferably, these products containcompounds containing such salt linkage at levels of at least about 10%by weight of the product, more preferably at least about 20% by weight,more preferably at least about 35% by weight, more preferably at leastabout 50% by weight, and still more preferably at least about 75% byweight.

The reactions between components (A)(I) and (A)(II), and (B)(I) and(B)(II) are carried out under salt forming conditions using conventionaltechniques. Typically, components (A)(I) and (A)(II), and (B)(I) and(B)(II), respectively, are mixed together and heated to a temperature inthe range of about 20° C. up to the decomposition temperature of thereaction component and/or product having the lowest such temperature,preferably about 50° C. to about 130° C., more preferably about 80° C.to about 110° C.; optionally, in the presence of a normally liquid,substantially inert organic liquid solvent/diluent, until the desiredproduct has formed.

The following examples illustrate the preparation of the saltcompositions of this invention. Unless otherwise indicated, in thefollowing examples and elsewhere in the specification and claims, allparts and percentages are by weight, and all temperatures are in degreescentigrade.

EXAMPLE 1

2228 parts of polyisobutylene (number average molecular weight=950)substituted succinic anhydride are heated to 90° C. with stirring. 178parts of dimethylethanolamine are added dropwise over a period of onehour while maintaining the temperature at 90°-97° C. The mixture ismaintained at 90°-97° C. for an additional 0.5 hour to provide thedesired product.

EXAMPLE 2

1600 parts of hydrocarbyl-substituted succinic anhydride derived from aC₁₆ alpha-olefin and maleic anhydride are heated to 80°-90° C. 445 partsof dimethylethanolamine are added over a period of one hour whilemaintaining the temperature at 85°-95° C. The mixture is maintained at85°-95° C. for an additional one hour, and then cooled to 60° C. toprovide the desired product.

EXAMPLE 3

2240 parts of the polyisobutylene substituted succinic anhydride used inExample 1 are heated to a temperature in the range of 110°-116° C. 174parts of morpholine are then added dropwise to the anhydride. Aftercompletion of the addition of morpholine, the resulting mixture ismaintained at a temperature of 116°-126° C. for two hours. 234 parts ofdiethylethanolamine are then added dropwise while the temperature ismaintained at 116°-126° C. After completion of the addition ofdiethylethanolamine, the resulting mixture is maintained at 116°-126° C.for 50 minutes with stirring. The resulting product is primarily anamide/salt.

EXAMPLE 4

A mixture of 1100 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 100 parts of Carbowax 200 (a product ofUnion Carbide identified as a polyethylene glycol having a molecularweight of 200) are heated to and then maintained at a temperature of123°-134° C., maintained at said temperature for 2 hours, then cooled to100° C. 117 parts of diethylethanolamine are added to the resultingproduct over a 0.2 hour period while maintaining the temperature at 100°C. The mixture is then cooled to room temperature. The product isprimarily an ester/salt.

EXAMPLE 5

A mixture of 1100 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 34 parts of pentaerythritol are heatedto a temperature of 125°-160° C., maintained at said temperature for 4hours, then adjusted to 130° C. 117 parts of diethylethanolamine areadded to the mixture. The temperature is maintained at 100°-130° C. for1 hour. The resulting product is then cooled to room temperature. Theproduct is primarily an ester/salt.

EXAMPLE 6

A mixture of 2240 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 300 parts of a 40 SUS mineral seal oilare heated to 50° C. with continuous stirring over a 0.5-hour period. 54parts of tap water are added and the resulting mixture is heated from50° C. to 92° C. over a 0.5-hour period, then maintained at 92°-98° C.for 5 hours. 244 parts of monoethanolamine are added and the resultingmixture is maintained at 92°-98° C. The product is primarily a di-salt.

EXAMPLE 7

A mixture of 2240 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 62 parts of ethylene glycol are heatedto a temperature in the range of 116°-120° C., then maintained at saidtemperature for 5 hours. The temperature of the mixture is thenincreased to a temperature in the range of 138°-146° C. and maintainedat said increased temperature for an additional 4.5 hours. Thetemperature of the mixture is then decreased to 115° C. over a period of0.5 hour. 122 parts of monoethanolamine are added to the mixture over aperiod of 0.5 hour while maintaining the temperature at 115°-120° C. Themixture is then stirred for an additional 0.5 hour while maintaining thetemperature at 115°-120° C. The resulting product is primarily anester/salt.

EXAMPLE 8

2895 parts of polyisobutylene (number average molecular weight=1700)substituted succinic anhydride are heated to 121° C. over a 1-hourperiod. 605 parts of diethylethanolamine are added dropwise over a2-hour period while maintaining the temperature of the mixture at121°-128° C. The mixture is maintained at 121°-123° C. for an additionalhour, and then cooled to 50° C. to provide the desired product. Theproduct is primarily an ester/salt.

EXAMPLE 9

A mixture of 1000 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 337 parts of a blend oil are heated to85° C. 26 parts of tap water are added to the mixture. The mixture isheated to 102° C. over a period of 0.25 hour. The mixture is maintainedat a temperature of 102°-105° C. for 4 hours, and then cooled to 70° C.209 parts of diethylethanolamine are added to the mixture over a0.2-hour period, and the mixture exotherms to 79° C. The mixture is thenmaintained at a temperature of 78°-79° C. for 1.5 hours and then cooledto provide the desired product. The product is primarily a di-salt.

EXAMPLE 10

1120 parts of the polyisobutylene-substituted succinic anhydride used inExample 1 are heated to 85°-90° C. over a 1-hour period. 117 parts ofdiethylethanolamine are added dropwise over a 0.5-hour period. Theresulting mixture is maintained at a temperature of 85°-90° C. for 4hours, then cooled to room temperature to provide the desired product.The product is primarily an internal salt.

EXAMPLE 11

A mixture of 917 parts of diluent oil, 40 parts of diatomaceous earthfilter aid, 10 parts of caustic soda, 0.2 part of a silicone-basedanti-foam agent, 135 parts of 3-amino-1,2,4-triazole, and 6.67 parts ofa commercial polyethylene polyamine mixture containing 33.5% nitrogenand substantially corresponding to tetraethylene pentamine are heated toa temperature of 121° C. with stirring. 1000 parts of thepolyisobutylene-substituted succinic anhydride used in Example 1 areslowly added to the mixture over a period of about one hour, and duringsuch addition the temperature of the mixture is increased from 121° C.to 154° C. The mixture is then maintained at a temperature of 154°-160°C. with nitrogen blowing for 12 hours. The mixture is then cooled to138°-149° C. and filtered. A final oil adjustment is made to adjust theproduct to a 45% by weight diluent oil. The product contains a minoramount of salt.

EXAMPLE 12

6720 parts of the polyisobutenyl succinic anhydride used in Example 1are heated to 90° C. with stirring. 702 parts of diethylethanolamine areadded over a 1.5-hour period. This intermediate mixture is then heatedfor an additional 0.5 hour at 90° C. Then 366 parts of monoethanolamineare slowly added. The mixture is maintained at 90° C. for 0.5 hour andthen cooled to provide a clear brown, viscous liquid product. Theproduct is a mixture of imide and salt, with minor amounts of amide andester being present.

EXAMPLE 13

2240 parts of the polyisobutenyl-substituted succinic anhydride used inExample 1 are heated to a temperature of about 90° C. 468 parts ofdiethylethanolamine are added over a 2-hour period. The mixture isheated for an additional hour at 90° C. to provide the desired product.The product is primarily an ester/salt.

EXAMPLE 14

A mixture of 2644 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 75 parts of ethylene glycol are heatedto a temperature of 120° C., and maintained at said temperature for 4hours. The temperature of the mixture is then increased to 160°-170° C.,maintained at said temperature for 2 hours, then reduced to 120° C. 281parts of diethylethanolamine are added to the mixture over a 15-minuteperiod. The temperature of the mixture is maintained at 115°-120° C. for1 hour. The mixture is then cooled to room temperature to provide thedesired product.

EXAMPLE 15

A mixture of 2240 parts of the polyisobutylene-substituted succinicanhydride used in Example 1 and 86 parts of piperazine are heated to atemperature of 116°-126° C. and maintained at said temperature for 2hours. 234 parts of diethylethanolamine are added dropwise to themixture. The temperature is maintained at 116°-126° C. for 50 minutes.The resulting product is then cooled to room temperature.

EXAMPLE 16

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1 are reacted with one equivalent of sodiumhydroxide under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 17

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1 are reacted with one equivalent of ammonia undersalt-forming conditions to form a desired salt composition.

EXAMPLE 18

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1 are reacted with one equivalent of calciumhydroxide under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 19

Two equivalents of the polyisobutylene-substituted succinic anhydrideidentified in Example 1 are reacted with one equivalent of sodiumhydroxide under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 20

Two equivalents of a C₂₀ hydrocarbyl-substituted succinic anhydride arereacted with one equivalent of dimethylethanolamine under salt-formingconditions to form a desired salt composition.

EXAMPLE 21

Two equivalents of a C₂₅₀ hydrocarbyl-substituted succinic anhydride arereacted with one equivalent of sodium hydroxide under salt-formingconditions to form a desired salt composition.

EXAMPLE 22

Two equivalents of a C₅₀₀ hydrocarbyl-substituted succinic anhydride arereacted with one equivalent of dimethylethanolamine under salt-formingconditions to form a desired salt composition.

EXAMPLE 23

One equivalent of a C₂₀ hydrocarbyl-substituted monocarboxylic acidderived from acrylic acid is reacted with one equivalent of ammoniaunder salt-forming conditions to form a desired salt composition.

EXAMPLE 24

One equivalent of a C₅₀₀ hydrocarbyl-substituted monocarboxylic acidderived from acrylic acid is reacted with one equivalent ofdiethylethanolamine under salt-forming conditions to form a desired saltcomposition

EXAMPLE 25

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₈ alpha-olefin and maleic anhydride are reacted with oneequivalent of sodium hydroxide under salt-forming conditions to form adesired salt composition.

EXAMPLE 25

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₁₂ alpha-olefin and maleic anhydride are reacted with oneequivalent of calcium hydroxide under salt-forming conditions to form adesired salt composition.

EXAMPLE 26

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₁₈ alpha-olefin and maleic anhydride are reacted with oneequivalent of ammonia under salt-forming conditions to form a desiredsalt composition.

EXAMPLE 28

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₁₆₋₁₈ alpha-olefin fraction and maleic anhydride are reactedwith one equivalent of sodium hydroxide under salt-forming conditions toform a desired salt composition.

EXAMPLE 29

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₁₂₋₁₆ alpha-olefin and maleic anhydride are reacted with oneequivalent of sodium carbonate under salt-forming conditions to form adesired salt composition.

EXAMPLE 30

Two equivalents of a oleic acid are reacted with one equivalent ofdiethylethanolamine under salt-forming conditions to form a desired saltcomposition.

EXAMPLE 31

Two equivalents of a hydrocarbyl-substituted succinic anhydride derivedfrom a C₁₄₋₁₈ alpha-olefin fraction and maleic anhydride are reactedwith one equivalent of ethylene diamine under salt-forming conditions toform a desired salt composition.

Explosive Compositions

The explosive compositions of the invention are water-in-oil emulsionswhich, in one embodiment, are cap-sensitive water-in-oil explosiveemulsions. These explosive emulsions employ the salt compositions (A)and (B) of the invention as emulsifiers. The inventive explosiveemulsions comprise a discontinuous oxidizer phase comprising at leastone oxygen-supplying component, a continuous organic phase comprising atleast one carbonaceous fuel, and an emulsifying amount of a mixture ofthe salt compositions (A) and (B).

The continuous organic phase is preferably present at a level of atleast about 2% by weight, more preferably in the range of from about 2%to about 15% by weight, more preferably in the range of from about 3.5%to about 8% by weight based on the total weight of explosive emulsion.The discontinuous oxidizer phase is preferably present at a level of atleast about 85% by weight, more preferably at a level in the range offrom about 85% to about 98% by weight, more preferably from about 92% toabout 96.5% by weight based on the total weight of said explosiveemulsion. The salt compositions (A) and (B) of the invention arepreferably present at a combined level in the range of from about 4% toabout 40% by weight, more preferably from about 12% to about 20% byweight based on the total weight of the organic phase. The weight ratioof (A) to (B) is preferably in the range of about 0.01:1 to about 100:1,more preferably about 0.1:1 to about 10:1. The oxygen-supplyingcomponent is preferably present at a level in the range of from about70% to about 95% by weight, more preferably from about 85% to about 92%by weight, more preferably from about 87% to about 90% by weight basedon the total weight of the oxidizer phase. The water is preferablypresent at a level in the range of about 5% to about 30% by weight, morepreferably about 8% to about 15% by weight, more preferably about 10% toabout 13% by weight based on the weight of the oxidizer phase.

The carbonaceous fuel that is useful in the explosive emulsions of theinvention can include most hydrocarbons, for example, paraffinic,olefinic, naphthenic, aromatic, saturated or unsaturated hydrocarbons,and is typically in the form of an oil or a wax or a mixture thereof. Ingeneral, the carbonaceous fuel is a water-immiscible, emulsifiablehydrocarbon that is either liquid or liquefied at a temperature of up toabout 95° C., and preferably between about 40° C. and about 75° C. Oilsfrom a variety of sources, including natural and synthetic oils andmixtures thereof can be used as the carbonaceous fuel.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral oils of theparaffinic, naphthenic, or mixed paraffin-naphthenic types. Oils derivedfrom coal or shale are also useful. Synthetic oils include hydrocarbonoils and halo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkyl benzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl) benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, alkylated polyphenyls, etc.); and the like.

Another suitable class of synthetic oils that can be used comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexylalcohol, ethylen glycol, diethylene glycol monoether, propylene glycol,pentaerythritol, etc.). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)-sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethyl-hexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, poly- aryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another class ofuseful oils. These include tetraethyl-silicate, tetraisopropylsilicate,tetra-(2-ethylhexyl)-silicate, tetra-(4-methylhexyl)-silicate,tetr(p-tert-butylphenyl)-silicate,hexyl-(4-methyl-2-pentoxy)-di-siloxane, poly(methyl)siloxanes,poly-(methylphenyl)-siloxanes, etc. Other useful synthetic oils includeliquid esters of phosphorus-containing acid (e.g., tricresyl phosphate,trioctyl phosphate, diethyl ester of decane phosphonic acid, etc.),polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type disclosed hereinabove can be used. Unrefined oils arethose obtained directly from a natural or synthetic source withoutfurther purification treatment. For example, a shale oil obtaineddirectly from a retorting operation, a petroleum oil obtained directlyfrom distillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except that they havebeen further treated in one or more purification steps to improve one ormore properties. Many such purification techniques are known to those ofskill in the art such as solvent extraction, distillation, acid or baseextraction, filtration, percolation, etc. Rerefined oils are obtained byprocesses similar to those used to obtain refined oils applied torefined oils which have been already used in service. Such rerefinedoils are also known as reclaimed or reprocessed oils and often areadditionally processed by techniques directed toward removal of spentadditives and oil breakdown products.

Examples of useful oils include a white mineral oil available from WitcoChemical Company under the trade designation KAYDOL; a white mineral oilavailable from Shell under the trade designation ONDINA; and a mineraloil available from Pennzoil under the trade designation N-750-HT.

The carbonaceous fuel can be any wax having melting point of at leastabout 25° C., such as petrolatum wax, microcrystalline wax, and paraffinwax, mineral waxes such as ozocerite and montan wax, animal waxes suchas spermacetic wax, and insect waxes such as beeswax and Chinese wax.Useful waxes include waxes identified by the trade designation MOBILWAX57 which is available from Mobil Oil Corporation; D02764 which is ablended wax available from Astor Chemical Ltd.; and VYBAR which isavailable from Petrolite Corporation. Preferred waxes are blends ofmicrocrystalline waxes and paraffin.

In one embodiment, the carbonaceous fuel includes a combination of a waxand an oil. In this embodiment, the wax content is at least about 25%and preferably ranges from about 25% to about 90% by weight of theorganic phase, and the oil content is at least about 10% and preferablyranges from about 10% to about 75% by weight of the organic phase. Thesemixtures are particularly suitable for use in cap-sensitive explosiveemulsions.

While its presence is not necessary, the explosive emulsions can alsocontain up to about 15% by weight of an auxiliary fuel, such asaluminum, aluminum alloys, magnesium, and the like. Particulate aluminumis a preferred auxiliary fuel.

The oxygen-supplying component is preferably at least one inorganicoxidizer salt such as ammonium, alkali or alkaline earth metal nitrate,chlorate or perchlorate. Examples include ammonium nitrate, sodiumnitrate, calcium nitrate, ammonium chlorate, sodium perchlorate andammonium perchlorate. Ammonium nitrate is especially preferred. Mixturesof ammonium nitrate and sodium or calcium nitrate are also preferred. Inone embodiment, inorganic oxidizer salt comprises principally ammoniumnitrate, although up to about 25% by weight of the oxidizer phase cancomprise either another inorganic nitrate (e.g., alkali or alkalineearth metal nitrate) or an inorganic perchlorate (e.g., ammoniumperchlorate or an alkali or alkaline earth metal perchlorate) or amixture thereof.

In one embodiment of the invention, closed-cell, void-containingmaterials are used as sensitizing components. The term "closed-cell,void-containing material" is used herein to mean any particulatematerial which comprises closed cell, hollow cavities. Each particle ofthe material can contain one or more closed cells, and the cells cancontain a gas, such as air, or can be evacuated or partially evacuated.In one embodiment of the invention, sufficient closed cell voidcontaining material is used to yield a density in the resulting emulsionof from about 0.8 to about 1.35 g/cc, more preferably about 0.9 to about1.3 g/cc, more preferably about 1.1 to about 1.3 g/cc. In general, theemulsions of the subject invention can contain up to about 15% byweight, preferably from about 0.25% to about 15% by weight of the closedcell void containing material. Preferred closed cell void containingmaterials are discrete glass spheres having a particle size within therange of about 10 to about 175 microns. In general, the bulk density ofsuch particles can be within the range of about 0.1 to about 0.4 g/cc.Useful glass microbubbles which can be used are the microbubbles sold by3M Company and which have a particle size distribution in the range offrom about 10 to about 160 microns and a nominal size in the range ofabout 60 to 70 microns, and densities in the range of from about 0.1 toabout 0.4 g/cc.; these include microbubbles distributed under the tradedesignation B15/250. Other useful glass microbubbles are sold under thetrade designation of ECCOSPHERES by Emerson & Cumming, Inc., andgenerally have a particle size range from about 44 to about 175 micronsand a bulk density of about 0.15 to about 0.4 g/cc. Other suitablemicrobubbles include the inorganic microspheres sold under the tradedesignation of Q-CEL by Philadelphia Quartz Company. The closed cellvoid containing material can be made of inert or reducing materials. Forexample, phenol-formaldehyde microbubbles can be utilized within thescope of this invention. If the phenol-formaldehyde microbubbles areutilized, the microbubbles themselves are a fuel component for theexplosive and their fuel value should be taken into consideration whendesigning a water-in-oil emulsion explosive composition. Another closedcell void containing material which can be used within the scope of thesubject invention is the saran microspheres sold by Dow ChemicalCompany. The saran microspheres have a diameter of about 30 microns anda particle density of about 0.032 g/cc. Because of the low bulk densityof the saran microspheres, it is preferred that only from about 0.25 toabout 1% by weight thereof be used in the water-in-oil emulsions of thesubject invention.

Gas bubbles which are generated in-situ by adding to the composition anddistributing therein a gas-generating material such as, for example, anaqueous solution of sodium nitrite, can also be used can be used tosensitize the explosive emulsions. Other suitable sensitizing componentswhich may be employed alone or in addition to the foregoing includeinsoluble particulate solid self-explosives such as, for example,grained or flaked TNT, DNT, RDX and the like and water-soluble and/orhydrocarbon-soluble organic sensitizers such as, for example, aminenitrates, alkanolamine nitrates, hydroxyalkyl nitrates, and the like.The explosive emulsions of the present invention may be formulated for awide range of applications. Any combination of sensitizing componentsmay be selected in order to provide an explosive composition ofvirtually any desired density, weight-strength or critical diameter. Thequantity of solid self-explosive ingredients and of water-soluble and/orhydrocarbon-soluble organic sensitizers may comprise up to about 40% byweight of the total explosive composition. The volume of the occludedgas component may comprise up to about 50% of the volume of the totalexplosive composition.

Optional additional materials may be incorporated in the explosiveemulsions of the invention in order to further improve sensitivity,density, strength, rheology and cost of the final explosive. Typical ofmaterials found useful as optional additives include, for example,particulate non-metal fuels such as sulfur, gilsonite and the like,particulate inert materials such as sodium chloride, barium sulphate andthe like, water phase or hydrocarbon phase thickeners such as guar gum,polyacrylamide, carboxymethyl or ethyl cellulose, biopolymers, starches,elastomeric materials, and the like, crosslinkers for the thickenerssuch as potassium pyroantimonate and the like, buffers or pH controllerssuch as sodium borate, zinc nitrate and the like, crystals habitmodifiers such as alkyl naphthalene sodium sulphonate and the like,liquid phase extenders such as formamide, ethylene glycol and the likeand bulking agents and additives of common use in the explosives art.The quantities of optional additional materials used may comprise up toabout 50% by weight of the total explosive emulsion.

The general criteria for cap-sensitivity is that the explosive besensitive to a No. 8 blasting cap at a cartridge diameter of 1.25 inchunder normal temperature conditions. The cap-sensitive explosiveemulsions of the present invention are shelf stable, which means theyexhibit shelf stability of at least six months and typically one year ormore.

A preferred method for making the explosive emulsions of the inventioncomprises the steps of (1) mixing water, inorganic oxidizer salts (e.g.,ammonium nitrate) and, in certain cases, some of the supplementalwater-soluble compounds, in a first premix, (2) mixing the carbonaceousfuel, the emulsifying salt compositions (A) and (B) of the invention andany other optional oil-soluble compounds, in a second premix and (3)adding the first premix to the second premix in a suitable mixingapparatus, to form a water-in-oil emulsion. The first premix is heateduntil all the salts are completely dissolved and the solution may befiltered if needed in order to remove any insoluble residue. The secondpremix is also heated to liquefy the ingredients. Any type of apparatuscapable of either low or high shear mixing can be used to prepare thesewater-in-oil emulsions. Closed- cell void containing materials,gas-generating materials, solid self-explosive ingredients such asparticulate TNT, solid fuels such as aluminum or sulfur, inert materialssuch as barytes or sodium chloride, undissolved solid oxidizer salts andother optional materials, if employed, are added to the emulsion andsimply blended until homogeneously dispersed throughout the composition.

The water-in-oil explosive emulsions of the invention can also beprepared by adding the second premix liquefied organic solution phase tothe first premix hot aqueous solution phase with sufficient stirring toinvert the phases. However, this method usually requires substantiallymore energy to obtain the desired dispersion than does the preferredreverse procedure. Alternatively, these water-in-oil explosive emulsionsare particularly adaptable to preparation by a continuous mixing processwhere the two separately prepared liquid phases are pumped through amixing device wherein they are combined and emulsified.

The salt compositions (A) and (B) of this invention can be addeddirectly to the inventive explosive emulsions. They can also be dilutedwith a substantially inert, normally liquid organic diluent such asmineral oil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate which can then be added to the explosive emulsions. Theseconcentrates usually contain a combined total of from about 10% to about90% by weight of the salt compositions (A) and (B), and may contain, inaddition, one or more other additives known in the art or describedhereinabove.

An advantage of the present invention is that by using the combinationof salt compositions (A) and (B) of the present invention asemulsifiers, explosive emulsions can be provided in gelatinous orsemi-gelatinous forms that are dry to the touch and cuttable. These areimportant characteristics when using these explosive emulsions in thepreparation of cap-sensitive explosive emulsions, particularly when suchcap-sensitive explosive emulsions are used in the manufacture ofexplosive cartridges, especially small diameter (i.e., diameters ofabout 1.25 inches or smaller) cartridges.

Explosive cartridges within the scope of this invention can be madeusing techniques well known in the art. The cap-sensitive explosiveemulsions of the invention are particularly suitable for makingcartridges on cartridging machines such as the type available fromNiepmann under the trade designation ROLLEX.

The following Examples A-I are illustrative of cap-sensitivewater-in-oil explosive emulsions within the scope of the invention.These emulsions, which are identified in Table I below, are prepared asfollows. The organic phase is prepared using the wax and oil indicatedin Table I and the product of Example 1. The oxidizer phase contains78.5% NH₄ NO₃, 10.7% NaNO₃, and 10.8% H₂ O. The weight ratio of theoxidizer phase to the organic phase is 95/5. The organic phase is meltedat 90° C. The oxidizer phase is heated to 104° C. The oxidizer phase isadded to the organic phase with stirring using a Sunbeam Mixmaster mixerat 50-100% on the variac for one minute. The emulsions are mixed or"worked" an additional six minutes in the Sunbeam Mixmaster mixer at100% on the variac. The viscosity of each emulsion and initial emulsiontemperatures are indicated in Table I. A sample of each emulsion isstored at 49° C. for 4 days and then at 70° C. for 2 days. After thattime the emulsions are removed and stored at room temperature. Thestability of each emulsion is observed overtime and reported in Table I.The penetration of the samples is measured using a 159 gram cone andapparatus.

                  TABLE I                                                         ______________________________________                                                     A       B       C     D     E                                    ______________________________________                                        Product of Ex. 1,                                                             (% of organic phase)                                                                       --      10      --    15    --                                   Product of Ex. 2,                                                             (% of organic phase)                                                                       10      10      5     5     3.3                                  Product of Ex. 13,                                                            (% or organic phase)                                                                       10      --      15    --    16.7                                 Mineral oil,                                                                  (% of organic phase)                                                                       20      20      20    20    20                                   50:50 blend of micro-                                                         crystalline wax and                                                           paraffin wax,                                                                 (% of organic phase)                                                                       60      60      60    60    60                                   Initial Viscosity                                                             (cPs × 10.sup.3 /°F.)                                                         118/    88/     99/   85/   130/                                              174     162     160   160   160                                  Avg. Penetration at                                                           Room Temp. (mm)                                                                            9.43    10.03   10.2  9.4   8.56                                 Storage Stability @                                                           Room Temp.                                                                    (Appearance/Days)                                                                          OK/21   OK/21   OK/19 OK/19 OK/6                                 Storage Stability @                                                           120° F.                                                                (Appearance/Days)                                                                          --      --      --    --    OK/6                                 Storage Stability @                                                           158° F.                                                                (Appearance/Days)                                                                          --      --      --    --    OK/6                                 ______________________________________                                                     F        G        H      I                                       ______________________________________                                        Product of Ex. 1,                                                             (% of organic phase)                                                                       16.7     --       17.2   16                                      Product of Ex. 2,                                                             (% of organic phase)                                                                       3.3      2.8      2.8    4                                       Product of Ex. 13,                                                            (% or organic phase)                                                                       --       17.2     --     --                                      Mineral oil,                                                                  (% of organic phase)                                                                       20       20       20     20                                      50:50 blend of micro-                                                         crystalline wax and                                                           paraffin wax,                                                                 (% of organic phase)                                                                       60       60       60     60                                      Initial Viscosity                                                             (cPs × 10.sup.3 /°F.)                                                         100/     99/      130/   100/                                                 170      158      160    160                                     Avg. Penetration at                                                           Room Temp. (mm)                                                                            6.9      8.93     10.1   9.5                                     Storage Stability @                                                           Room Temp.                                                                    (Appearance/Days)                                                                          OK/6     OK/14    OK/14  OK/6                                    Storage Stability @                                                           120° F.                                                                (Appearance/Days)                                                                          OK/6     --       --     OK/6                                    Storage Stability @                                                           158° F.                                                                (Appearance/Days)                                                                          OK/6     --       --     OK/6                                    ______________________________________                                    

Each of the emulsions identified in Table I are dry to the touch andcuttable, and exhibit good stability to high temperatures

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

I claim:
 1. An explosive composition comprising a discontinuous oxidizerphase comprising at least one oxygen-supplying component, a continuousorganic phase comprising at least carbonaceous fuel, and an emulsifyingamount of(A) at least one salt composition derived from (A)(I) at leastone high-molecular weight hydrocarbyl-substituted carboxylic acid oranhydride, or ester or amide derivative of said acid or anhydride, thehydrocarbyl substituent of (A)(I) having an average of from about 20 toabout 500 carbon atoms, and (A)(II) ammonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound; and (B) at least one salt compositionderived from (B)(I) at least one low-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederivative of said acid or anhydride, the hydrocarbyl substituent of(B)(I) having an average of from about 8 to about 18 carbon atoms, and(B)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound.
 2. The composition of claim 1 wherein (A)(I) is derived fromat least one alpha-beta olefinically unsaturated carboxylic acid oranhydride, or ester or amide derivative of said acid or anhydride, saidacid or anhydride or derivative containing up to about 20 carbon atomsper molecule exclusive of the carboxyl-based groups.
 3. The compositionof claim 1 wherein (A)(I) is a monocarboxylic acid or anhydride, orester or amide derivative of said acid or anhydride.
 4. The compositionof claim 1 wherein (A)(I) is a polycarboxylic acid or anhydride, orester or amide derivative of said acid or anhydride.
 5. The compositionof claim 1 wherein (A)(I) is represented by the formulae ##STR21##wherein R is said hydrocarbyl substituent of (A)(I).
 6. The compositionof claim 1 wherein component (A)(I) is an ester or an amide derived fromat least one compound represented by the formulae ##STR22## wherein R issaid hydrocarbyl substituent of (A)(I).
 7. The composition of claim 1wherein said hydrocarbyl substituent of (A)(I) has an average of fromabout 30 to about 500 carbon atoms per molecule.
 8. The composition ofclaim 1 wherein said hydrocarbyl substituent of (A)(I) has an average offrom about 40 to about 500 carbon atoms per molecule.
 9. The compositionof claim 1 wherein said hydrocarbyl substituent of (A)(I) has an averageof from about 50 to about 500 carbon atoms per molecule.
 10. Thecomposition of claim 1 wherein said hydrocarbyl substituent of (A)(I) isan alkyl or an alkenyl group.
 11. The composition of claim 1 whereinsaid hydrocarbyl substituent of (A)(I) is a poly(isobutylene) group. 12.The composition of claim 1 wherein component (A)(I) comprises at leastone amide derived from at least one primary amine, secondary amineand/or ammonia.
 13. The composition of claim 1 wherein component (A)(I)comprises at least one amide derived from at least one primary orsecondary monoamine.
 14. The composition of claim 1 wherein component(A)(I) comprises at least one amide derived from a polyamine containingat least one primary and/or secondary amino group.
 15. The compositionof claim 1 wherein component (A)(I) comprises at least one amide derivedfrom at least one alkylene polyamine of the formula ##STR23## wherein nis a number in the range of from 1 to about 10, each R is independentlya hydrogen atom or a hydrocarbyl group or a hydroxy-substitutedhydrocarbyl group having up to about 700 carbon atoms, and the Alkylenegroup has from 1 to about 10 carbon atoms.
 16. The composition of claim1 wherein component (A)(I) comprises at least one ester derived from atleast one monohydric alcohol.
 17. The composition of claim 1 whereincomponent (A)(I) comprises at least one ester derived from at least onepolyhydric alcohol.
 18. The composition of claim 1 wherein component(A)(I) comprises at least one ester derived from at least one compoundrepresented by the formula

    R(OH).sub.m

wherein R is a monovalent or polyvalent organic group joined to the OHgroups through carbon-to-oxygen bonds and m is an integer of from 1 toabout
 10. 19. The composition of claim 1 wherein component (A)(I)comprises at least one ester and/or amide derived from at least onehydroxyamine.
 20. The composition of claim 1 wherein component (A)(I)comprises at least one ester and/or amide derived from (a) at least oneN-(hydroxyl-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 21. The composition of claim 1 wherein component(A)(I) comprises at least one ester and/or amide derived from at leastone alkanol amine containing up to about 40 carbon atoms.
 22. Thecomposition of claim 1 wherein component (A)(I) comprises at least oneester and/or amide derived from at least one compound selected from thegroup consisting of (a) primary or secondary amines which can berepresented correspondingly by the formulae ##STR24## (b)hydroxyl-substituted oxyalkylene analogs of said alkanol aminesrepresented by the formulae ##STR25## wherein R is independently ahydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of any of the above.
 23. The composition ofclaim 1 wherein component (A)(I) comprises at least one ester derivedfrom at least one compound selected from the group consisting of (a)tertiary alkanol amines represented by the formula ##STR26## (b)hydroxyl-substituted oxyalkylene analogs of said tertiary alkanol aminesrepresented by the formula ##STR27## wherein each R is independently ahydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of the above.
 24. The composition of claim 1wherein component (A)(II) comprises at least one monoamine.
 25. Thecomposition of claim 1 wherein component (A)(II) comprises at least onepolyamine.
 26. The composition of claim 1 wherein component (A)(II)comprises at least one primary, secondary and/or tertiary amine.
 27. Thecomposition of claim 1 wherein component (A)(II) comprises at least onealiphatic, cycloaliphatic and/or aromatic amine.
 28. The composition ofclaim 1 wherein component (A)(II) comprises at least one alkylenepolyamine of the formula ##STR28## wherein n is a number of from 1 toabout 10, each R is independently a hydrogen atom or a hydrocarbyl groupor a hydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, and the Alkylene group has from 1 to about 10 carbon atoms. 29.The composition of claim 1 wherein component (A)(II) comprises (a) atleast one N-(hydroxyl-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 30. The composition of claim 1 wherein component(A)(II) comprises at least one alkanol amine containing up to about 40carbon atoms.
 31. The composition of claim 1 wherein component (A)(II)is selected from the group consisting of (a) primary, secondary andtertiary alkanol amines which can be represented correspondingly by theformulae ##STR29## (b) hydroxyl-substituted oxyalkylene analogs of saidalkanol amines represented by the formulae ##STR30## wherein each R isindependently a hydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of any of the above.
 32. The composition ofclaim 1 wherein component (A)(II) is dimethylethanolamine ordiethylethanolamine.
 33. The composition of claim 1 wherein component(A)(II) is ammonia.
 34. The composition of claim 1 wherein component(A)(II) comprises at least one alkali metal.
 35. The composition ofclaim 1 wherein component (A)(II) comprises sodium.
 36. The compositionof claim 1 wherein component (A)(II) comprises at least one alkalineearth metal.
 37. The composition of claim 1 wherein component (A)(II)comprises at least one alkali metal oxide, hydroxide or carbonate. 38.The composition of claim 1 wherein component (A)(II) comprises at leastone alkaline earth metal oxide, hydroxide or carbonate.
 39. Thecomposition of claim 1 wherein (B)(I) is a monocarboxylic acid oranhydride, or ester or amide derivative of said acid or anhydride. 40.The composition of claim 1 wherein (B)(I) is a polycarboxylic acid oranhydride, or ester or amide derivative of said acid or anhydride. 41.The composition of claim 1 wherein (B)(I) is represented by the formulae##STR31## wherein R is said hydrocarbyl substituent of (B)(I).
 42. Thecomposition of claim 1 wherein component (B)(I) is an ester or an amidederived from at least one compound represented by the formulae ##STR32##wherein R is said hydrocarbyl substituent of (B)(I).
 43. The compositionof claim 1 wherein said hydrocarbyl substituent of (B)(I) is derivedfrom at least one compound selected from the group consisting of1-octene, styrene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,tetra-propylene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene and 1-octadecene.
 44. The composition ofclaim 1 wherein said hydrocarbyl substituent of (B)(I) is derived fromat least one member within the alpha-olefin fraction selected from thegroup consisting of C₁₅₋₁₈ alpha olefins, C₁₂₋₁₆ alpha-olefins, C₁₄₋₁₆alpha-olefins, C₁₄₋₁₈ alpha-olefins and C₁₆₋₁₈ alpha-olefins.
 45. Thecomposition of claim 1 wherein said hydrocarbyl substituent of (B)(I)has an average of from about 12 to about 18 carbon atoms.
 46. Thecomposition of claim 1 wherein said hydrocarbyl substituent of (B)(I)has an average of from about 16 to about 18 carbon atoms.
 47. Thecomposition of claim 1 wherein said hydrocarbyl substituent of (B)(I) isan alkyl or an alkenyl group.
 48. The composition of claim 1 whereincomponent (B)(I) comprises at least one amide derived from at least oneprimary amine, secondary amine and/or ammonia.
 49. The composition ofclaim 1 wherein component (B)(I) comprises at least one amide derivedfrom at least one primary or secondary monoamine.
 50. The composition ofclaim 1 wherein component (B)(I) comprises at least one amide derivedfrom a polyamine containing at least one primary and/or secondary aminogroup.
 51. The composition f claim 1 wherein component (B)(I) comprisesat least one amide derived from at least one alkylene polyamine of theformula ##STR33## wherein n is a number in the range of from 1 to about10, each R is independently a hydrogen atom or a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, and the Alkylene group has from 1 to about 10 carbon atoms. 52.The composition of claim 1 wherein component (B)(I) comprises at leastone ester derived from at least one monohydric alcohol.
 53. Thecomposition of claim 1 wherein component (B)(I) comprises at least oneester derived from at least one polyhydric alcohol.
 54. The compositionof claim 1 wherein component (B)(I) comprises at least one ester derivedfrom at least one compound represented by the formula

    R(OH).sub.m

wherein R is a monovalent or polyvalent organic group joined to the OHgroups through carbon-to-oxygen bonds and m is an integer of from 1 toabout
 10. 55. The composition of claim 1 wherein component (B)(I)comprises at least one ester and/or amide derived from at least onehydroxyamine.
 56. The composition of claim 1 wherein component (B)(I)comprises at least one ester and/or amide derived from (a) at least oneN-(hydroxyl-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 57. The composition of claim 1 wherein component(B)(I) comprises at least one ester and/or amide derived from at leastone alkanol amine containing up to about 40 carbon atoms.
 58. Thecomposition of claim 1 wherein component (B)(I) comprises at least oneester and/or amide derived from at least one compound selected from thegroup consisting of (a) primary or secondary amines which can berepresented correspondingly by the formulae ##STR34## (b)hydroxyl-substituted oxyalkylene analogs of said alkanol aminesrepresented by the formulae ##STR35## wherein R is independently ahydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of any of the above.
 59. The composition ofclaim 1 wherein component (B)(I) comprises at least one ester derivedfrom at least one compound selected from the group consisting of (a)tertiary alkanol amines represented by the formula ##STR36## (b)hydroxyl-substituted oxyalkylene analogs of said tertiary alkanol aminesrepresented by the formula ##STR37## wherein each R is independently ahydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more of the above.
 60. The composition of claim 1wherein component (B)(II) comprises at least one monoamine.
 61. Thecomposition of claim 1 wherein component (B)(II) comprises at least onepolyamine.
 62. The composition of claim 1 wherein component (B)(II)comprises at least one primary, secondary and/or tertiary amine.
 63. Thecomposition of claim 1 wherein component (B)(II) comprises at least onealiphatic, cycloaliphatic and/or aromatic amine.
 64. The composition ofclaim 1 wherein component (B)(II) comprises at least one alkylenepolyamine of the formula ##STR38## wherein n is a number of from 1 toabout 10, each R is independently a hydrogen atom or a hydrocarbyl groupor a hydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, and the Alkylene group has from 1 to about 10 carbon atoms. 65.The composition of claim 1 wherein component (B)(II) comprises (a) atleast one N-(hydroxy-substituted hydrocarbyl) amine, (b) at least onehydroxyl-substituted poly(hydrocarbyloxy) analog of (a), or (c) amixture of (a) and (b).
 66. The composition of claim 1 wherein component(B)(II) comprises at least one alkanol amine containing up to about 40carbon atoms.
 67. The composition of claim 1 wherein component (B)(II)is selected from the group consisting of (a) primary, secondary andtertiary alkanol amines which can be represented correspondingly by theformulae ##STR39## (b) hydroxyl-substituted oxyalkylene analogs of saidalkanol amines represented by the formulae ##STR40## wherein each R isindependently a hydrocarbyl group of one to about 8 carbon atoms or ahydroxyl-substituted hydrocarbyl group of 2 to about 8 carbon atoms andR' is a divalent hydrocarbyl group of 2 to about 18 carbon atoms, and(c) mixtures of two of more thereof.
 68. The composition of claim 1wherein component (B)(II) is dimethylethanolamine ordiethylethanolamine.
 69. The composition of claim 1 wherein component(B)(II) is ammonia.
 70. The composition of claim 1 wherein component(B)(II) comprises at least one alkali metal.
 71. The composition ofclaim 1 wherein component (B)(II) comprises sodium.
 72. The compositionof claim 1 wherein component (B)(II) comprises at least one alkalineearth metal.
 73. The composition of claim 1 wherein component (B)(II)comprises at least one alkali metal oxide, hydroxide or carbonate. 74.The composition of claim 1 wherein component (B)(II) comprises at leastone alkaline earth metal oxide, hydroxide or carbonate.
 75. Thecomposition of claim 1 wherein the weight ratio of component (A) tocomponent (B) is from about 0.01:1 to about 100:1.
 76. An explosivecomposition made by combining an oxidizer phase comprising at least oneoxygen-supplying component, an organic phase comprising at least onecarbonaceous fuel, and an emulsifying amount of(A) at least one saltcomposition derived from (A)(I) at least one high-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederivative of said acid or anhydride, the hydrocarbyl substituent of(A)(I) having an average of from about 20 to about 500 carbon atoms, and(A)(II) ammonia at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound; and (B) at least one salt composition derived from (B)(I) atleast one low-molecular weight hydrocarbyl-substituted carboxylic acidor anhydride, or ester or amide derivative of said acid or anhydride,the hydrocarbyl substituent of (B)(I) having an average of from about 8to about 18 carbon atoms, and (B)(II) ammonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound.
 77. An explosive composition comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, and an emulsifying amount of(A) at least one saltderived from (A)(I) at least one hydrocarbyl-substituted carboxylic acidor anhydride, the hydrocarbyl substituent of (A)(I) having an average offrom about 50 to about 500 carbon atoms, and (A)(II)dimethylethanolamine or diethylethanolamine; and (B) at least one saltderived from (B)(I) at least one hydrocarbyl-substituted carboxylic acidor anhydride, the hydrocarbyl substituent of (B)(I) having an average offrom about 8 to about 18 carbon atoms, and (B)(II) dimethylethanolamineor diethylethanolamine.
 78. An explosive composition made by combiningan oxidizer phase comprising at least one oxygen-supplying component, anorganic phase comprising at least one carbonaceous fuel, and anemulsifying amount of(A) at least one salt derived from (A)(I) at leastone hydrocarbyl-substituted carboxylic acid or anhydride, thehydrocarbyl substituent of (A)(I) having an average of from about 50 toabout 500 carbon atoms, and (A)(II) dimethylethanolamine ordiethylethanolamine; and (B) at least one salt derived from (B)(I) atleast one hydrocarbyl-substituted carboxylic acid or anhydride, thehydrocarbyl substituent of (B)(I) having an average of from about 8 toabout 18 carbon atoms, and (B)(II) dimethylethanolamine ordiethylethanolamine.
 79. A cap-sensitive explosive emulsion comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, said carbonaceous fuel comprising at least one wax,and an emulsifying amount of(A) at least one salt composition derivedfrom (A)(I) at least one high-molecular weight hydrocarbyl-substitutedcarboxylic acid or anhydride, or ester or amide derivative of said acidanhydride, the hydrocarbyl substituent of (A)(I) having an average offrom about 20 to 500 carbon atoms, and (A)(II) ammonia, at least oneamine, at least one alkali or alkaline earth metal, and/or at least onealkali or alkaline earth metal compound; and (B) at least one saltcomposition derived from (B)(I) at least one low-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederivative of said acid or anhydride, the hydrocarbyl substituent of(B)(I) having an average of from about 8 to about 18 carbon atoms, and(B)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound.
 80. A cap-sensitive explosive emulsion comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, said carbonaceous fuel comprising at least one wax,and an emulsifying amount of(A) at least one salt derived from (A)(I) atleast one hydrocarbyl-substituted carboxylic acid or anhydride, thehydrocarbyl substituent of (A)(I) having an average of from about 50 toabout 500 carbon atoms, and (A)(II) dimethylethanolamine ordiethylethanolamine; and (B) at least one salt derived from (B)(I) atleast one hydrocarbyl-substituted carboxylic acid or anhydride, thehydrocarbyl substituent of (B)(I) having an average of from about 8 toabout 18 carbon atoms, and (B)(II) dimethylethanolamine ordiethylethanolamine.
 81. A cartridge comprising a tubular containercontaining at least one explosive emulsion, said emulsion comprising adiscontinuous oxidizer phase comprising at least one oxygen-supplyingcomponent, a continuous organic phase comprising at least onecarbonaceous fuel, said carbonaceous fuel comprising at least one wax,and an emulsifying amount of(A) at least one salt composition derivedfrom (A)(I) at least one high-molecular weight hydrocarbyl-substitutedcarboxylic acid or anhydride, or ester or amide derivative of said acidor anhydride, the hydrocarbyl substituent of (A)(I) having an average offrom about 20 to about 500 carbon atoms, and (A)(II) ammonia, at leastone amine, at least one alkali or alkaline earth metal, and/or at leastone alkali or alkaline earth metal compound; and (B) at least one saltcomposition derived from (B)(I) at least one low-molecular weighthydrocarbyl-substituted carboxylic acid or anhydride, or ester or amidederivative of said acid or anhydride, the hydrocarbyl substituent of(B)(I) having an average of from about 8 to about 18 carbon atoms, and(B)(I) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound.
 82. A cartridge having a diameter of about 1.25 inches orsmaller comprising at least one cap-sensitive explosive emulsion, saidemulsion comprising a discontinuous oxidizer phase comprising at leastone oxygen-supplying component, a continuous organic phase comprising atleast one carbonaceous fuel, and an emulsifying amount of(A) at leastone salt composition derived from (A)(I) at least one high-molecularweight hydrocarbyl-substituted carboxylic acid or anhydride, or ester oramide derivative of said acid or anhydride, the hydrocarbyl substituentof (A)(I) having an average of from about 20 to about 500 carbon atoms,and (A)(II) ammonia, at least one amine, at least one alkali or alkalineearth metal, and/or at least one alkali or alkaline earth metalcompound; and (B) at least one salt composition derived from (B)(I) atleast one low-molecular weight hydrocarbyl-substituted carboxylic acidor anhydride, or ester or amide derivative of said acid or anhydride,the hydrocarbyl substituent of (B)(I) having an average of from about 8to about 18 carbon atoms, and (B)(II) ammonia, at least one amine, atleast one alkali or alkaline earth metal, and/or at least one alkali oralkaline earth metal compound.